JP7282012B2 - Chemical composition for ground injection - Google Patents

Description

The present invention relates to a chemical solution composition for ground injection, and in particular, using a prepolymer of an aliphatic polyisocyanate compound, a urethane-based composition that can give a high-strength solidified body, has excellent reaction activity, and has little environmental pollution. It relates to a rock consolidation chemical.

Conventionally, inorganic or organic systems have been used as one of the measures adopted in ground improvement applications for stabilizing and strengthening unstable bedrock and ground, and in cavity filling applications for filling cracks and voids in artificial structures. A method is known in which grout is injected to solidify the natural ground or the like. For example, Japanese Patent Application Laid-Open No. 4-283290 discloses that one such grout is a sodium silicate aqueous solution (A), A polyisocyanate composition (B) comprising a polyisocyanate and a reactive diluent that does not react with the polyisocyanate but is hydrolyzed with an aqueous sodium silicate solution and reacts with the aqueous sodium silicate solution and/or the polyisocyanate. Injectable drug solution compositions are known. In Japanese Patent Laid-Open No. 5-78667, a liquid A containing water and an alkali metal salt of silicic acid as a main component and a liquid B containing an isocyanate prepolymer as a main component are combined as rock consolidation chemicals. A two-liquid foaming urethane resin has been clarified, and furthermore, in JP-A-2016-175982, liquid A, which is prepared by blending water glass and a polyol, and further adding water, and polyisocyanate as essential components In the two-component rock solidification chemical solution consisting of B solution and B solution, the water content in such A solution is regulated, and the water and polyol are prepared so that they have a predetermined ratio, and a dispersant is added. A structure with further addition has been proposed.

Various organic isocyanate compounds having two or more isocyanate groups in the molecule and modified products (prepolymers) thereof can be used as the polyisocyanate, which is the main component of liquid B in these consolidation chemicals. However, from the viewpoint of reaction activity and strength of the resulting solid, practically, diphenylmethane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (crude MDI), polymeric MDI, tolylene diisocyanate ( Aromatic polyisocyanate compounds such as TDI) are used. However, when liquid B, which is composed of an aliphatic polyisocyanate compound such as hexamethylene diisocyanate or isophorone diisocyanate as a polyisocyanate component, is combined with liquid A as described above to form a consolidating chemical solution. However, the reaction between liquid A and liquid B is slow, so when stopping a large amount of water leakage or spring water, part of the injected chemical flows out together with the water leakage or spring water, making the water cloudy. In addition to causing problems such as foaming and foaming, which have an adverse effect on the environment, the strength of the solidified body formed by the reaction of A and B is not sufficient. It was not able to fully meet the purpose of stabilizing reinforcement and cavity filling.

JP-A-4-283290 JP-A-5-78667 JP 2016-175982 A

Against the background of the above-described circumstances, the present inventors have made various studies on consolidation chemicals using aliphatic isocyanate compounds as polyisocyanates. At the same time, by using at least a primary and/or secondary amino group-containing compound as the active hydrogen group-containing compound in liquid A, the above-mentioned problems when using an aliphatic isocyanate compound can be completely resolved. The discovery led to the completion of the present invention.

Therefore, the problem to be solved by the present invention is to provide a urethane-based ground injection chemical composition that is excellent in reaction activity and causes little environmental pollution. To provide a urethane-based ground consolidation chemical liquid which can form a cohesion and does not cause problems such as cloudiness and foaming when it comes into contact with water such as leakage or spring water.

In order to solve the above-described problems, the present invention can be suitably implemented in various aspects as listed below. Adoptable. It should be noted that the aspects and technical features of the present invention are not limited to those described below, and can be understood based on the inventive idea grasped from the description of the entire specification. It should be.

First, the first aspect of the present invention is a ground consisting of a liquid A containing an aqueous silicate solution, an active hydrogen group-containing compound, and a catalyst as essential components, and a liquid B containing polyisocyanate as an essential component. In the liquid medicine composition for injection, as the polyisocyanate, an aliphatic polyisocyanate prepolymer is contained in the liquid B, and as the active hydrogen group-containing compound, at least a primary and/or secondary amino group-containing compound. is contained in the above liquid A.

In a second aspect of the present invention, a polyamine compound having two or more primary and/or secondary amino groups in one molecule is used as the primary and/or secondary amino group-containing compound. be.

Furthermore, a third aspect according to the present invention is that the polyamine compound has an aromatic ring.

In addition, in the fourth aspect of the present invention, the primary and / or secondary amino group-containing compound is 0.5 to 50 parts by mass with respect to 100 parts by mass of the aliphatic polyisocyanate prepolymer , is contained.

A fifth aspect according to the present invention is to use a tertiary amine catalyst as the catalyst.

A sixth aspect of the present invention is that the catalyst is contained in a proportion of 0.1 to 30 parts by mass with respect to 100 parts by mass of the aliphatic polyisocyanate prepolymer.

Furthermore, the seventh aspect of the present invention is configured such that the aliphatic polyisocyanate prepolymer has a monomer content of less than 5% by mass.

Additionally, in an eighth aspect according to the present invention, said aliphatic polyisocyanate prepolymer is selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, isophorone diisocyanate, and bis(isocyanatomethyl)cyclohexane. the adduct, biuret, allophanate, or isocyanurate derived from the polyisocyanate compound.

Furthermore, a ninth aspect of the present invention is that the A liquid and the B liquid each have a viscosity of 5000 mPa·s or less at a temperature of 25°C.

According to such a configuration of the chemical composition for ground injection according to the present invention, various effects as listed below can be exhibited.
(1) A urethane-based natural ground consolidation chemical with excellent reaction activity and low environmental pollution is provided, and the use of such a chemical can advantageously form a high-strength solidified body.
(2) Since the hardening reaction proceeds immediately after the injection of the chemical solution, it is possible to suppress the outflow of the chemical solution to the environment, and advantageously reduce the cloudiness and foaming of water leakage and spring water.
(3) Since the chemical solution contains a silicate, it has excellent flame retardancy and excellent safety during construction, and the resulting concretions also have high flame retardancy.
(4) By using an aliphatic polyisocyanate prepolymer as the polyisocyanate, which is an essential component of liquid B, it is possible to form a strong solidified body and effectively prevent contamination of the working environment at the injection site. can be suppressed or avoided.

In short, the present invention provides a two-part urethane-based chemical composition comprising liquid A and liquid B, in which, together with the aqueous silicate solution and the catalyst, which are essential components of liquid A, as an active hydrogen group-containing compound, 1 While containing at least a class and/or secondary amino group-containing compound, an aliphatic polyisocyanate prepolymer is contained as the polyisocyanate which is an essential component in the liquid B, thereby producing an aliphatic polyisocyanate Even with a compound, excellent reaction activity can be effectively realized, and a high-strength solidified body can be advantageously formed. It has great features where it is obtained.

In the liquid A, which is one of the two liquids constituting the chemical composition according to the present invention, the silicate aqueous solution contained as one of its essential components is a soluble silicic acid compound. It is an aqueous solution and is also called so-called water glass. Examples of the silicate compound include sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, lithium silicate, and ammonium silicate. Therefore, easily available and inexpensive sodium silicate (sodium silicate) is preferably used. When sodium silicate is used, the SiO ₂ /Na ₂ O molar ratio is preferably in the range of 2.0 to 4.0. When this molar ratio is less than 2.0, the compatibility with additives such as active hydrogen group-containing compounds and reaction catalysts deteriorates, and the formation of gel-like matter is likely to occur, making long-term storage difficult. It becomes. On the other hand, if the molar ratio is more than 4.0, the dispersion stability of the liquid is lowered and the solidification point is further increased, which may cause problems such as the inability to use in winter.

By the way, various kinds of water glass, which is an aqueous solution of sodium silicate as described above, are commercially available, and in the present invention, such commercially available products can be appropriately selected and used. The aqueous solution of sodium silicate is specified in JIS standard (JIS K 1408) and is known as No. 1, No. 2, No. 3, etc. In addition, it is formulated in accordance with this JIS standard. 4, 5, or 1.5, 2.5, etc., can be used as long as they are used. Furthermore, the ratio of solid components in the water glass in the form of such an aqueous solution varies depending on the number of JIS standards, the type of water glass, etc., but the stability of liquid A and solidification From the point of view of properties and the like, water glass containing a solid content of about 20 to 60% by mass, preferably 30 to 50% by mass, is advantageously used.

In addition, an active hydrogen group-containing compound is further used as another of the essential components constituting the liquid A. In the present invention, at least one of such active hydrogen group-containing compounds As one, primary and/or secondary amino group-containing compounds, which are amine compounds with primary and/or secondary amino groups, will be used. Here, the primary and/or secondary amino group-containing compound is not particularly limited as long as it is a compound containing a primary and/or secondary amino group. polyamine compounds, aromatic amine compounds, aromatic polyamine compounds, amino acids, alkanolamines, and the like.

Specifically, aliphatic amine compounds include linear amino group-containing compounds such as butylamine, octylamine and dodecylamine, alicyclic amino group-containing compounds such as cyclohexylamine, and cyclic amino group-containing compounds such as piperidine. Examples of aliphatic polyamines include linear amino group-containing compounds such as butanediamine, hexanediamine, octanediamine, polyetheramine, triethylenetetramine, and tetraethylenepentamine, cyclohexanediamine, Alicyclic amino group-containing compounds such as norbornene diamine, cyclic amino group-containing compounds such as piperazine, and aromatic ring-containing aliphatic amino group-containing compounds such as xylylenediamine can be mentioned. Examples of aromatic amine compounds include amino group-containing compounds such as aniline, toluidine, anisidine and methylaniline. Examples of aromatic polyamine compounds include toluenediamine, methylenedianiline, diaminodiphenyl ether, trimethylphenylenediamine, diethyltoluenediamine, dimethylthiotoluenediamine, N,N'-bis(sec-butylamino)diphenylmethane, aminobenzylamine, Amino group-containing compounds such as methylenebis(ethylmethylaniline) can be mentioned. Furthermore, amino acids include compounds containing a carboxyl group and an amino group in the molecule, such as lysine, valine, and asparagine. In addition, alkanolamine compounds include ethanolamine, hexanolamine, diethanolamine, and the like. A compound having an amino group and a hydroxyl group in the molecule can be mentioned. These amine compounds having primary and/or secondary amino groups may be used alone, or may be used in combination of two or more.

Further, in the present invention, the above-mentioned primary and/or secondary amino group-containing compound has two or more primary and/or secondary amino group-containing compounds in one molecule in order to effectively exhibit its function as a cross-linking agent. Or it is preferably a polyamine compound having a secondary amino group, and in particular, it is preferably an amine compound having an aromatic ring in terms of improving properties such as reactivity and flame retardancy, more preferably an aromatic Among them, an aromatic polyamine compound having a structure in which at least one of the positions adjacent to the amino groups bonded to the aromatic ring is substituted with an alkyl group is particularly preferably used.

Further, such a primary and / or secondary amino group-containing compound is generally in a proportion of 0.5 to 50 parts by mass with respect to 100 parts by mass of the aliphatic polyisocyanate prepolymer in the B liquid. , preferably in the A solution, more preferably 0.8 to 40 parts by mass, more preferably 1 to 30 parts by mass. If the content is less than 0.5 parts by mass, the reaction between the amino groups in the primary and/or secondary amino group-containing compound and the isocyanate groups in the aliphatic polyisocyanate prepolymer becomes insufficient, If the strength of the solidified body obtained is insufficient or the reaction does not proceed sufficiently, problems such as liquid leakage or outflow of the chemical solution into running water will occur. In addition, when the content exceeds 50 parts by mass, it becomes excessive with respect to the aliphatic polyisocyanate prepolymer, and there is a risk of causing outflow into the environment, and primary and / or secondary amino groups Since the contained compound itself is expensive, it causes a problem of poor economy.

As the active hydrogen group-containing compound, in addition to the amine compound as described above, various known active hydrogen group-containing compounds can be used. Polyols will preferably be used.

Such polyols are not particularly limited, and those conventionally used as polyol components in rock solidification chemicals can be similarly used, for example, known polyethers Polyols, polyester polyols and the like can be mentioned. These polyols can be used singly or in combination as appropriate. Although the polyether polyol is not particularly limited, for example, polyhydric alcohols having at least two or more active hydrogen groups, such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc. Amines such as ethylenediamine; Alkanolamines such as ethanolamine and diethanolamine are used as starting materials, and those produced by the addition reaction of these compounds with alkylene oxides such as ethylene oxide and propylene oxide can be used. I can. In addition, polyester polyols are not particularly limited. polycarboxylic acid-based polyester polyols obtained by reacting with polycarboxylic acids, lactone-based polyester polyols obtained by ring-opening polymerization of lactones, and castor oil-based polyester polyols.

In addition, the liquid A according to the present invention contains various known catalysts, that is, reaction catalysts, as essential components. will be

Here, the tertiary amine catalyst includes a foaming catalyst that promotes the reaction between polyisocyanate and water when foaming is intended by contact with water, and a foaming catalyst that promotes the reaction between polyisocyanate and polyol. There are a resinification catalyst having an action, an isocyanurate catalyst having an action to promote the trimerization of polyisocyanate, and the like, and they are all appropriately selected from known ones.

Specifically, the foaming catalyst includes N,N,N′,N″,N″-pentamethyldiethylenetriamine, N,N,N′-triethylaminoethylethanolamine, bis(dimethylaminoethyl) ether, N , N,N′-trimethylaminoethylpiperazine, N,N-dimethylaminoethoxyethanol, triethylamine and the like. Further, the resinification catalyst includes N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropanediamine, N,N,N',N'-tetramethylhexane. Diamine, 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. Furthermore, examples of the isocyanuration catalyst include 2,4,6-tris(dimethylaminomethyl)phenol, N,N',N''-tris(dimethylaminopropyl)-hexahydro-s-triazine, and the like. The catalysts may be used singly or in combination of two or more, and among these, foaming catalysts or resin-forming catalysts are preferably used.

In addition to the tertiary amine catalysts described above, metal catalysts, quaternary ammonium salts, and the like can also be used as catalysts contained in liquid A. Here, as the metal catalyst, known ones can be used without any particular limitation. Examples include organic acid metal salts such as sodium, potassium, calcium, tin, lead, bismuth, zinc, iron, nickel, zirconium and cobalt, Organometallic complexes can be used. Among them, examples of organic acid metal salts include salts of acetic acid, octylic acid, neodecanoic acid, naphthenic acid, rosin acid and the like with the above metals, and examples of organometallic complexes include acetylacetone and the like with the above metals. complexes of Specifically, sodium acetate, potassium acetate, potassium octylate, bismuth octylate, lead octylate, iron octylate, tin octylate, calcium octylate, zinc octylate, zirconium octylate, bismuth neodecanoate, zinc neodecanoate , lead neodecanoate, cobalt neodecanoate, dibutyltin dioctate, dibutyltin dilaurate; iron acetylacetonate, zinc acetylacetonate, zirconium acetylacetonate, nickel acetylacetonate, and tin acetylacetonate. These metal salts and metal complexes may be dissolved in diluents such as mineral spirits, organic acids, glycols, esters, etc. in order to improve handling properties. Moreover, these metal catalysts may be used alone or in combination of two or more. Among these, potassium, tin, lead, bismuth or zinc acetate, octylate, neodecanoate, laurate and acetylacetone complexes are preferred, and potassium, tin and bismuth are more preferred as metals. The used catalyst will be used suitably.

Quaternary ammonium salts include tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, propyltrimethylammonium, butyltrimethylammonium, pentyltrimethylammonium, hexyltrimethylammonium, heptyltrimethylammonium, octyltrimethylammonium, nonyltrimethylammonium, decyl Trimethylammonium, undecyltrimethylammonium, dodecyltrimethylammonium, tridecyltrimethylammonium, tetradecyltrimethylammonium, heptadecyltrimethylammonium, hexadecyltrimethylammonium, heptadecyltrimethylammonium, octadecyltrimethylammonium and other aliphatic ammonium compounds, (2- hydroxypropyl)trimethylammonium, hydroxyethyltrimethylammonium, hydroxyammonium compounds such as trimethylaminoethoxyethanol, 1-methyl-1-azania-4-azabicyclo[2,2,2]octanium, 1,1-dimethyl-4-methyl alicyclic ammonium compounds such as piperidinium, 1-methylmorpholinium, 1-methylpiperidinium, and the like; Among these, tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, butyltrimethylammonium, hexyltrimethylammonium, octyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium, tetradecyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, (2-hydroxypropyl)trimethylammonium, hydroxyethyltrimethylammonium, 1-methyl-1-azania-4-azabicyclo[2,2,2]octanium, and 1 , 1-dimethyl-4-methylpiperidinium will preferably be used.

Examples of organic or inorganic acid groups constituting such quaternary ammonium salts include formic acid, acetic acid, octylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid. Organic acid groups such as acid groups, benzoic acid groups, toluic acid groups, ethylbenzoic acid groups, methyl carbonate groups, phenol groups, alkylbenzenesulfonic acid groups, toluenesulfonic acid groups, benzenesulfonic acid groups, phosphate ester groups, and halogen inorganic acid groups such as radicals, hydroxyl groups, hydrogen carbonate groups, and carbonate groups. Among these, a formic acid group, an acetic acid group, an octylic acid group, a methyl carbonate group, a halogen group, a hydroxyl group, a hydrogen carbonate group, and a carbonate group are preferable because of their excellent catalytic activity and industrial availability.

Various types of catalysts comprising such quaternary ammonium salts are commercially available. 410, Kaorizer No. 420 (manufactured by Kao Corporation) and the like.

By the way, the amount of catalyst contained in such liquid A is generally 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, per 100 parts by weight of the aliphatic polyisocyanate prepolymer. It will be determined by the proportion of the part. If the content of the catalyst is less than 0.1 parts by mass, the contribution to the reaction is reduced, and there is a problem that the development of strength is delayed. A problem arises in which speed control becomes difficult.

On the other hand, as polyisocyanate, which is an essential component of liquid B, which is the other one of the two liquids constituting the chemical composition for ground injection targeted by the present invention, in the present invention, Instead of using the aliphatic polyisocyanate compound itself, an aliphatic polyisocyanate prepolymer derived from such an aliphatic polyisocyanate compound is used. Here, the aliphatic polyisocyanate prepolymer is not particularly limited, and examples thereof include polyisocyanate compounds such as pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, and isophorone diisocyanate. is preferably used as an adduct, biuret, or allophanate obtained by reacting with an active hydrogen group-containing compound, or an isocyanurate obtained by trimerizing such a polyisocyanate compound. The isocyanurate may contain a dimeric uretdione without any problem. For such aliphatic polyisocyanate prepolymers, isocyanurates are more preferably used in consideration of properties such as strength and flame retardancy of solidified bodies.

Such an aliphatic polyisocyanate prepolymer is generally contained in the B liquid at a rate of 50 to 100% by mass, preferably 70 to 100% by mass, more preferably 80 to 100% by mass. It will happen. If the content of the aliphatic polyisocyanate prepolymer is less than 50% by mass, there is a problem that the strength of the solidified body is lowered. , it is also possible to constitute the B liquid only with such an aliphatic polyisocyanate prepolymer.

In addition, since such an aliphatic polyisocyanate prepolymer is obtained by using and modifying the aliphatic polyisocyanate compound as described above, the modified prepolymer contains fat as a raw material. group polyisocyanate compound remains as a monomer component, but in the present invention, such a residual monomer component is preferably 5% by mass or less, particularly 1% by mass or less. Thus, an aliphatic polyisocyanate prepolymer is prepared. If the amount of such residual monomer components increases, physical properties such as the strength of the solidified body are lowered, and the monomer components volatilize during construction, causing problems such as deterioration of the working environment.

By the way, it is possible to add conventional additives to the above-described liquids A and B, which constitute the rock solidification chemical solution according to the present invention, according to the purpose of use. For example, additives for liquid A include foaming agents, foam stabilizers, flame retardants, viscosity reducing agents, and the like. As an additive for liquid A, it is used in a proportion of 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, per 100 parts by mass of the aliphatic polyisocyanate prepolymer. Additives for liquid B include foam stabilizers, flame retardants, viscosity reducers, and the like. .05 to 5 parts by mass, preferably 0.1 to 3 parts by mass, the viscosity reducing agent is 0.5 to 60 parts by mass with respect to 100 parts by mass of the aliphatic polyisocyanate prepolymer , Preferably used in a proportion of 1 to 40 parts by mass, and the flame retardant is 1 to 50 parts by mass, preferably 5 to 40 parts by mass with respect to 100 parts by mass of the aliphatic polyisocyanate prepolymer It will be used as follows.

Among these additives, known foaming agents such as water, hydrocarbons, hydrofluorocarbons, hydrofluoroolefins, and hydrochlorofluoroolefins can be used. This foaming agent is not particularly limited, but water is preferably used. This water is also supplied from the silicate aqueous solution that constitutes the liquid A, and reacts with the polyisocyanate of the liquid B to generate carbon dioxide gas, so that it functions as a blowing agent. is.

Also, the foam stabilizer is used to uniformly arrange the cell structure of the foam formed by the reaction of the A liquid and the B liquid. Examples of foam stabilizers include silicones, nonionic surfactants, polyoxyalkylene-modified dimethylpolysiloxanes, polysiloxaneoxyalkylene copolymers, polyoxyethylene sorbitan fatty acid esters, castor oil ethylene oxide adducts, and lauryl fatty acid ethylene oxide adducts. Among these, silicones 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 dimethylpolysiloxanes, polysiloxaneoxyalkylene copolymers, and the like are preferable.

Furthermore, examples of flame retardants include brominated flame retardants, chlorine flame retardants, phosphorus flame retardants, halogenated phosphate esters, and inorganic flame retardants. These may be used independently and may be used in combination of 2 or more types. Among these, phosphoric acid esters and halogenated phosphoric acid esters are preferably used in that they have less impact on the environment and also function as viscosity reducing agents for foamable compositions. Examples of phosphoric acid esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trixylenyl phosphate, and the like. Examples of halogenated phosphates include tris(chloroethyl) phosphate, tris(2-chloropropyl) phosphate, tris(dichloropropyl) phosphate, tetrakis(2-chloroethyl) dichloroisopentyl diphosphate, polyoxyalkylene bis(dichloro alkyl) phosphate and the like.

In addition, the viscosity reducing agent is used as a solvent, dissolved in liquid A or B, and has the function of reducing the viscosity of these liquids, as long as it has such a function, especially Examples include, but are not limited to, alcohols such as methanol and ethanol, ethers such as ethyl cellosolve and butyl cellosolve, cyclic esters such as propylene carbonate, dicarboxylic acid methyl esters, and esters such as ethylene glycol monomethyl ether acetate. and petroleum hydrocarbons. These may be used alone or in combination of two or more.

By the way, each of the A liquid and the B liquid prepared according to the present invention is adjusted so that the viscosity at a temperature of 25° C. is 5000 mPa·s or less, preferably 20 to 3000 mPa·s. If this viscosity is higher than 5000 mPa·s, the liquids A and B become viscous liquids, and the fluidity during mixing deteriorates, and the fluidity during pumping also deteriorates, which may cause an increase in injection pressure. It will cause some problems. If the viscosity is lower than 20 mPa·s, it is likely to be diluted with water, and problems such as white turbidity of waste water are likely to occur. In addition, the A liquid and B liquid may be temperature-controlled using a heater in order to reduce the viscosity during pumping, and are heated to 0 to 50 ° C. according to the outside temperature. It is also possible.

In addition, when using the chemical composition for soil injection according to the present invention, which is composed of liquid A and liquid B, the two liquids are mixed at the time of use and applied to the target ground, bedrock, etc. A high-strength consolidated body is formed by pouring and reaction curing according to known techniques. The mixing ratio (A:B) of liquid A and liquid B can be appropriately changed depending on the content of hydroxyl groups in liquid A and the content of NCO groups in liquid B. , A:B=2:1 to 1:3, preferably within the range of 1:1 to 1:2. In addition, there are no particular restrictions on the method of using these liquids A and B, as long as the two liquids can be reliably mixed immediately before their use, and various conventionally known injection techniques can be used. will be adopted as appropriate.

Further, the reaction time (the time from mixing to curing) when liquid A and liquid B are mixed is preferably within 300 seconds, more preferably 20 to 240 seconds. If this reaction time is longer than 300 seconds, the chemical solution will flow out into the spring water before it solidifies after being injected into the natural ground, causing problems such as cloudiness and foaming of the water. If the reaction time is too short, for example, shorter than 20 seconds, the reaction proceeds too much, causing problems such as clogging the injection pipe of the chemical solution and difficulty in penetrating the ground sufficiently. become.

Some examples and comparative examples of the present invention are shown below to clarify the present invention more specifically, but the present invention is not subject to any restrictions by the description of such examples. It goes without saying that it is nothing. In addition to the following examples and the specific descriptions above, the present invention includes various changes and modifications based on the knowledge of those skilled in the art as long as they do not depart from the spirit of the present invention. , improvements, etc. may be added.

In addition to the characteristics (viscosity) of the liquids A and B obtained in the following examples and comparative examples, the expansion ratio and the expansion ratio of the reaction product when the liquids A and B are mixed and cured by reaction. The reaction time, the combustibility of the reaction product, the compressive strength of the reaction product, the degree of cloudiness of the water after reaction and foaming in water, and the degree of foaming of the waste liquid obtained after the reaction and foaming in water. , respectively, were measured or evaluated according to the following methods. "%" and "parts" shown below are both based on mass.

(1) Measurement of Viscosity The viscosities of liquids A and B obtained in Examples and Comparative Examples were measured using a B-type viscometer according to JIS-K-7117-1.

(2) Measurement of foaming ratio Liquids A and B adjusted to a temperature of 20°C were each weighed at a predetermined mixing ratio shown in Tables 1 to 4 below so that the total amount was 100 ml, They were placed in a 2 L disc cup and thoroughly mixed and agitated to cure. Then, the foaming height of the reaction product after completion of the curing reaction was measured to obtain the foaming ratio.

(3) Measurement of reaction time Liquid A and liquid B adjusted to a temperature of 20 ° C. are mixed at the mixing ratio shown in Tables 1 to 4 to initiate the reaction, and then the reaction formed Measure the time until gas is generated from the product and the foaming height stops changing, or the time until the reaction product is pierced with a skewer and does not stick to the inside, whichever is later is the reaction time. bottom.

(4) Turbidity test under foaming in water Liquid A and liquid B adjusted to a temperature of 20°C were weighed and mixed at the mixing ratio shown in Tables 1 to 4 so that the total amount was 100 ml. . Then, immediately after the mixing, the mixture of liquids A and B was put into 1 L of water at 20° C. contained in a 2 L disk cup and allowed to stand until the reaction stopped. After the completion of the reaction, the state of the water was visually observed. ◎ indicates that no white turbidity was observed immediately after the reaction subsided. ○, the case where white turbidity was observed even after 5 minutes or more after the reaction subsided, was evaluated as ×.

(5) Compressive Strength Test Liquids A and B adjusted to a temperature of 20° C. were weighed and mixed at a mixing ratio shown in Tables 1 to 4 so that the total amount was 100 ml. Next, immediately after such mixing, a predetermined amount of the mixture of liquid A and liquid B is put into a bottomed cylindrical mold with an inner diameter of 50 mm and a height of 100 mm so that the foaming ratio is 3 times, After closing the lid, it was cured for 2 hours or longer. Thereafter, the demolded reaction product was cured at 20° C. for 24 hours or more, and the compressive strength was measured according to JIS-K-7220:2006.

(6) Combustion test (flame retardancy evaluation)
Liquid A and liquid B adjusted to a temperature of 20 ° C. are mixed at the mixing ratio shown in Tables 1 to 4, and a predetermined amount of the resulting chemical solution is poured into a mold of 200 mm × 200 mm × 50 mm, Free foaming was allowed. Then, after curing for 24 hours or more, a test piece having a thickness of 13 mm, a length of 150 mm, and a width of 50 mm was cut out from the obtained reaction product, and JIS-A-9511: 6.13 flammability of 2017. A combustion test was performed according to test method B. In the evaluation, ⊚ indicates that the combustion time is 90 seconds or less and the combustion length is 60 mm or less; Or, those with a burning length of 60 mm or more were evaluated as x.

(7) Foaming Test of Drainage Liquids A and B adjusted to a temperature of 20° C. were weighed and mixed at the mixing ratio shown in Tables 1 to 4 so that the total amount was 100 ml. Then, immediately after such mixing, the mixture of liquids A and B was put into 1 L of water at 20° C. contained in a 2 L disk cup and allowed to stand for 2 hours. Furthermore, after this standing, the water in contact with the reaction product in the disc cup is collected as waste water, and the waste liquid is diluted to 100 times the concentration, placed in a screw tube, and shaken for 10 seconds. I did. Then, after the end of this shaking, if bubbles are not confirmed in the screw tube within 30 seconds, it is evaluated as ⊚, if bubbles are not confirmed within 60 seconds, it is ○, and if bubbles can be confirmed for 60 seconds or more, it is evaluated as ×. bottom.

First, the following various raw materials were prepared as components of liquid A or liquid B used in the following examples and comparative examples.
Silicate aqueous solution: No. 2 sodium silicate (manufactured by Fuji Chemical Co., Ltd., molar ratio: 2.5, solid content: 40%)
: No. 1 sodium silicate (manufactured by Fuji Chemical Co., Ltd., molar ratio: 2.1, solid content: 48%)
Active hydrogen group-containing compound (primary or secondary amino compound)
: Diethyltoluenediamine (Ethacure 100 manufactured by Albemarle, containing a primary amino group)
: Dimethylthiotoluenediamine (Ethacure 300 manufactured by Albemarle, containing a primary amino group)
: 2,6-diaminotoluene (manufactured by Tokyo Chemical Industry Co., Ltd., containing a primary amino group)
: 4,4'-methylenebis(N-sec-butylaniline) (Etacure 420 manufactured by Albemarle, containing a secondary amino group)
: N,N'-dibenzylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd., containing a secondary amino group)
: Polyetheramine (Baxxodur EC310 manufactured by BASF, containing primary amino group)
Polyol: polyoxypropylene glycol (propylene glycol-based polyether polyol: PP2000 manufactured by Sanyo Chemical Industries, Ltd., molecular weight: 2000, hydroxyl value: 110 mgKOH/g)
: Ethylenediamine-based polyether polyol (N P300 manufactured by Sanyo Chemical Industries, Ltd., molecular weight: 300, hydroxyl value: 750 mgKOH/g)
Catalyst: N,N,N',N'',N''-pentamethyldiethylenetriamine (Kao Riser No. 3 manufactured by Kao Corporation)
: 70% bis(dimethylaminoethyl) ether/30% dipropylene glycol (Kao Riser No. 12 manufactured by Kao Corporation)
: N,N-dimethylaminohexanol (Kao Riser No. 25 manufactured by Kao Corporation)
Aliphatic isocyanate compound: HDI (1) (Mitsui Chemicals Takenate D-170N, isocyanurate of hexamethylene diamine diisocyanate)
: HDI (2) (Takenate D-160N manufactured by Mitsui Chemicals, Inc., TMP adduct of 75% hexamethylenediamine diisocyanate, 25% ethyl acetate solution)
: HDI (3) (Takenate D-165N manufactured by Mitsui Chemicals, Inc., biuret form of hexamethylene diamine diisocyanate)
: HDI (4) (manufactured by Mitsui Chemicals, Inc. Takenate D-178NL, allophanate form of hexamethylenediamine diisocyanate)
: PDI (Stabio D-376N manufactured by Mitsui Chemicals, Inc., isocyanurate form of pentamethylenediamine diisocyanate)
: H ₆ XDI (Mitsui Chemicals Takenate D-127N, 75% bis(iso
cyanatomethyl)cyclohexane isocyanurate in 25% ethyl acetate
liquid)
: IPDI (Takenate D-140N manufactured by Mitsui Chemicals, Inc., trimethylolpropane adduct of isophorone diisocyanate, 25% ethyl acetate solution)
: HDI (5) (manufactured by Tokyo Chemical Industry Co., Ltd., hexamethylene diisocyanate)
Flame retardant: TMCPP (manufactured by Daihachi Chemical Co., Ltd., tris (2-chloropropyl) phosphate)
Foam stabilizer: polyether-modified siloxane (S Z-1671 manufactured by Dow Corning Toray Silicone Co., Ltd.)

(Examples 1 to 27)
-Preparation of liquid A-
The various raw materials prepared above, that is, the silicate aqueous solution, the active hydrogen group-containing compound, the polyol compound, and the catalyst, are uniformly mixed in various combinations and blending ratios shown in Tables 1 to 4 below. At least, various A liquid formulations according to Examples 1 to 27 were respectively prepared. Then, the viscosity of the obtained liquid A composition was measured, and the results are shown in Tables 1 to 4 below.

-Preparation of B solution-
The various raw materials prepared above, that is, the aliphatic isocyanate compound, the foam stabilizer and the flame retardant, were uniformly mixed in various combinations and blending ratios shown in Tables 1 to 4 below, and Examples 1 to 27 were prepared. , were prepared respectively. Then, the viscosity of the resulting composition containing liquid B was measured, and the results are shown in Tables 1 to 4 below.

- Reaction of A liquid and B liquid -
The A liquid and the B liquid obtained above are combined in the parts by mass shown in Tables 1 to 4, mixed uniformly at room temperature, reacted, and various evaluation tests are performed according to the evaluation method described above. and the results are shown in Tables 1 to 4 below.

(Comparative example 1)
In Example 1, each test was conducted according to the same procedure as in Example 1, except that no primary or secondary amine compound was added. The obtained results are shown in Table 4 below.

(Comparative example 2)
Each test was conducted in the same manner as in Comparative Example 1, except that 5 parts of polyoxypropylene glycol was added as the polyol compound in Comparative Example 1. The obtained results are shown in Table 4 below.

(Comparative Example 3)
In Example 1, each test was performed according to the same procedure as in Example 1, except that no reaction catalyst was added. The obtained results are shown in Table 4 below.

(Comparative Example 4)
Each test was conducted according to the same procedure as in Example 1, except that the aliphatic polyisocyanate prepolymer in Example 1 was replaced with the raw material, hexamethylene diisocyanate (monomer). The obtained results are shown in Table 4 below.

As is clear from the results of Tables 1 to 4, the chemical compositions of Examples 1 to 27, which consist of liquids A and B according to the present invention, all have a reaction time of 300 seconds or less. , It has excellent reaction activity, and at an expansion ratio of about 3 times or more, it can form a solidified body with high compressive strength and excellent flame retardancy. Excellent results were obtained.

On the other hand, it was found that the chemical compositions composed of liquids A and B prepared in Comparative Examples 1 to 4 took a long time for the curing reaction and were inferior in reaction activity. Further, in the chemical compositions according to Comparative Examples 1 and 2, since the primary and/or secondary amine compound as a cross-linking agent was not added to the A liquid, the A liquid and the B liquid were mixed. However, it did not crosslink and thicken, and therefore, when it was put into water and allowed to react, the chemical dissolved into the water, causing the water to become cloudy and foamy. Furthermore, in the chemical solution composition according to Comparative Example 3, since the reaction catalyst (tertiary amine) was not added, the solidified body obtained easily crumbled and became brittle. In the chemical solution composition of Comparative Example 4, as the polyisocyanate, the aliphatic polyisocyanate compound, which is the raw material monomer thereof, is used as it is, not the aliphatic polyisocyanate prepolymer. Even if a primary or secondary amine compound is added, cross-linking does not proceed, and only a brittle and easily crumbled solidified body similar to that of Comparative Example 3 is formed. admitted.

Claims (9)

A chemical solution composition for ground injection consisting of a solution A containing an aqueous silicate solution, an active hydrogen group-containing compound, and a catalyst as essential components, and a solution B containing a polyisocyanate as an essential component,
As the polyisocyanate, an aliphatic polyisocyanate prepolymer is contained in the liquid B, and at least a primary and/or secondary amino group-containing compound is contained in the liquid A as the active hydrogen group-containing compound. A chemical solution composition for ground injection, characterized by being squeezed. The ground injection according to claim 1, wherein the primary and/or secondary amino group-containing compound is a polyamine compound having two or more primary and/or secondary amino groups in one molecule. liquid medicine composition. 3. The chemical composition for ground injection according to claim 2, wherein the polyamine compound has an aromatic ring. The primary and/or secondary amino group-containing compound is contained in a proportion of 0.5 to 50 parts by mass with respect to 100 parts by mass of the aliphatic polyisocyanate prepolymer. The chemical composition for ground injection according to any one of claims 1 to 3. 5. The chemical composition for ground injection according to any one of claims 1 to 4, wherein the catalyst is a tertiary amine catalyst. 6. Any one of claims 1 to 5, wherein the catalyst is contained in a proportion of 0.1 to 30 parts by mass with respect to 100 parts by mass of the aliphatic polyisocyanate prepolymer. The chemical solution composition for ground injection according to the item. 7. The chemical composition for ground injection according to any one of claims 1 to 6, wherein the monomer content of the aliphatic polyisocyanate prepolymer is less than 5% by mass. The aliphatic polyisocyanate prepolymer is an adduct derived from an aliphatic polyisocyanate compound selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, isophorone diisocyanate, and bis(isocyanatomethyl)cyclohexane. , biuret, allophanate and isocyanurate, according to any one of claims 1 to 7. The ground injection according to any one of claims 1 to 8, wherein each of said A liquid and said B liquid has a viscosity of 5000 mPa s or less at a temperature of 25 ° C. liquid medicine composition.