JP6916043B2 - Chemical composition for ground injection - Google Patents

Description

The present invention relates to a chemical solution composition for ground injection, and more particularly to a chemical solution composition for ground injection which is suitably used for the ground where a large amount of water leakage or spring water occurs.

Inorganic or organic grout injection has traditionally been adopted as one of the measures adopted in ground improvement applications for stabilizing and strengthening unstable rocks and ground, and cavity filling applications for filling cracks and voids in artificial structures. There is, and it has a certain effect. For example, Patent Document 1 discloses, as one such grout, an injectable solution composition for stabilizing soil such as a polyol and / or an organic polyamine compound, an organic polyisocyanate compound, and water. However, the chemical composition described in Patent Document 1 cannot achieve sufficient solidification strength because the foaming ratio of the foam formed therein becomes high as a whole, and a large amount of water leakage or springing occurs. For water, there was an inherent problem that it was difficult to completely stop the water because the strength to support the water pressure could not be obtained.

Further, as a chemical composition for the purpose of stopping water against a large amount of water leakage or spring water, in Patent Document 2, a main agent containing an isocyanate component and a curing agent containing a castor oil-modified polyester polyol and a plasticizer component are used. The water blocking agent for the water-impervious sheet obtained by mixing with and is clarified. However, since this water blocking agent has a low viscosity due to a large amount of plasticizer, when it is injected into rock or the like, the bleed-out plasticizer is washed away into the spring water, which causes water pollution. It is inherent.

In addition, when injecting the chemical composition as described above in order to block (stop) the flow of spring water, after mixing the two solutions, by the time they react and foaming / hardening begins. However, due to the existence of this time lag, when injected into the ground with spring water, the chemical solution composition is mixed with water and diluted, so that the injected chemical solution composition also springs. It causes a problem that it is washed away by the flow of water and it is not possible to sufficiently stop the water, and a problem that the chemical composition that is washed away by the spring water causes water pollution. Therefore, as a countermeasure, in addition to increasing the viscosity of the chemical solution, it is conceivable to adopt means such as increasing the reaction speed, but when the viscosity is increased, the injection pressure when injecting the chemical solution becomes excessive. As a result, there is a problem that the load on the equipment and facilities becomes large, and when the reaction speed is increased, the curing becomes too fast, causing a problem that the chemical solution does not sufficiently penetrate into cracks and the ground. Will be done.

Japanese Unexamined Patent Publication No. 7-262363 Japanese Unexamined Patent Publication No. 2011-245453

Here, the present invention has been made in the background of the above-mentioned circumstances, and the problem to be solved thereof is a large amount of water leakage or spring water while advantageously ensuring an easy injection work of a chemical solution. Chemical solution composition for ground injection that can stop water without flowing out even underneath, effectively prevent the occurrence of cloudiness of water when it comes into contact with water, and can advantageously suppress the outflow of chemical solution. It is an attempt to provide things.

Then, in order to solve the above-mentioned problems, the present invention can be preferably carried out in various aspects as listed below, and each aspect described below can be carried out in any combination. It can be adopted. It should be noted that the aspects or technical features of the present invention are not limited to those described below, and are understood based on the invention idea grasped from the description of the entire specification. It should be.

(1) In a chemical solution composition for ground injection composed of a solution A containing an active hydrogen group-containing compound as a main component and a solution B containing a polyisocyanate as a main component, the active hydrogen group-containing compound has a hydroxyl group. A first active hydrogen group-containing compound composed of a polyol compound is contained in a proportion of 90% by mass or more, and at least a second active hydrogen group-containing compound having a faster reaction rate than the first active hydrogen group-containing compound is contained. 0.5% by mass of the second active hydrogen group-containing compound contained in the solution in which polyisocyanate and dioctyl phthalate were mixed in a volume ratio of 1: 1 without adding a catalyst. When added so as to have a content ratio, the increase in the viscosity of the solution 1 minute after the addition is 1.5 times or more the viscosity of the solution before the addition, and the solution A and the solution B are described. A chemical solution composition for ground injection, characterized in that the viscosity of the solution at 25 ° C. is 50 to 500 mPa · s, respectively.
(2) The polyol compound contains a polyether polyol obtained by adding an alkylene oxide to the initiator in a proportion of 90% by mass or more, and 95% by mass or more of the alkylene oxide added to the initiator is propylene oxide. The chemical composition for ground injection according to the above aspect (1), wherein the polyether polyol has a hydroxyl value of 30 to 300 mgKOH / g.
(3) The chemical composition for ground injection according to the above aspect (2), wherein the initiator is a polyhydric alcohol.
(4) The chemical composition for ground injection according to the above aspect (2) or the above aspect (3), wherein the polyether polyol has a molecular weight of 200 to 4000.
(5) The above-mentioned aspects (1) to (4), wherein the content ratio of the polyol obtained by using the amine compound as the initiator in the polyol compound is 5% by mass or less. The chemical composition for ground injection according to any one of the above.
(6) What of the above-described aspects (1) to (5), wherein the second active hydrogen group-containing compound is an amine compound having a primary amino group and / or a secondary amino group. The chemical composition for ground injection according to any one of them.
(7) The embodiment (1), wherein the second active hydrogen group-containing compound is contained so as to be contained in a proportion of 0.1 to 8% of the total amount of the active hydrogen group-containing compound. No. The chemical composition for ground injection according to any one of the above-mentioned aspects (6).
(8) Any one of the above-described embodiments (1) to (7), wherein the liquid A further contains at least one of a metal catalyst and a tertiary amine catalyst. The chemical composition for ground injection according to the above.
(9) The chemical composition for ground injection according to any one of the above-mentioned aspects (1) to (8), which gives a curing reaction product having an effervescence ratio of 2 times or less. ..
(10) Any of the above-described aspects (1) to (9), wherein the mixing ratio of the solution A and the solution B is 1: 0.5 to 1: 3 on a volume basis. The chemical composition for ground injection according to one of the above.

Then, according to such a configuration of the present invention, various effects as listed below can be achieved.
(1) When injecting a chemical solution, the water does not become cloudy even if it comes into contact with water, so that the injection work can be advantageously carried out.
(2) At the time of injection, the chemical solution is adjusted to a predetermined low viscosity until the solution A and the solution B are mixed with a mixer, so that the injection workability is remarkably excellent, and after the mixing, the chemical solution is remarkably excellent in injection workability. Immediately, a reaction product that is difficult to be diluted with water is formed, and elution into spring water is effectively suppressed or prevented, so that the reaction product is difficult to be washed away by water.
(3) Since the chemical solution is effectively prevented from being diluted with water and washed away, water pollution is advantageously prevented, and the deterioration of the physical properties of the reaction product due to the chemical solution being washed away is caused. It will be effectively prevented.

In short, according to the present invention, in a two-component type chemical solution composition for ground injection composed of solution A and solution B, the active hydrogen group-containing compound as the main component of the solution A is a polyol compound having a hydroxyl group. By containing the active hydrogen group-containing compound of 90% by mass or more and further containing a predetermined second active hydrogen group-containing compound having a high reaction rate, the first active hydrogen group is contained. Utilizing the difference in reactivity of the compound and the second active hydrogen group-containing compound with respect to polyisocyanate, it is configured so that a chemical composition that is difficult to be diluted in spring water can be formed even immediately after mixing. It has a great feature when it achieves its intended purpose. Then, the liquid A and the liquid B are specifically composed as follows.

<Liquid A>
(First active hydrogen group-containing compound)
First, the active hydrogen group-containing compound that occupies the main component of the liquid A is composed of at least a predetermined first active hydrogen group-containing compound and a second active hydrogen group-containing compound, wherein the first activity is carried out. As the hydrogen group-containing compound, any known polyol compound having a hydroxyl group can be used. The polyol compound is used in a proportion of 90% by mass or more of the total amount of the active hydrogen group-containing compound including the first and second active hydrogen group-containing compounds, whereby the object of the present invention is advantageously realized. It can be done. Among them, a polyether polyol is preferably used as the first active hydrogen group-containing compound. Further, such a polyether polyol is not particularly limited, and various ones conventionally used as a polyol component in a chemical composition can be used in the same manner. For example, it can be appropriately selected and used from various known polyether polyols. In addition, such a polyether polyol can be used alone, or a plurality of such polyether polyols can be appropriately combined and used in combination.

The polyether polyol is not particularly limited, but has a multivalent value such as a compound having at least two or more active hydrogen groups, for example, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like. Alcohols; amines such as ethylenediamine; produced by adding or addition-polymerizing an alkylene oxide such as ethylene oxide or propylene oxide to a compound such as alkanolamines such as ethanolamine and diethanolamine as an initiator. Those and the like will be preferably used. Here, the polyol compound which is the first active hydrogen group-containing compound may be composed of the above-mentioned polyether polyol alone, or other known polyols (for example, polyester polyol, acrylic polyol, polymer). It may be mixed with (polyol, etc.), but in order to advantageously obtain the action and effect according to the present invention, 90% by mass or more, preferably 95% by mass or more of the polyol compound is made of a polyether polyol. Is desirable.

Further, in the present invention, among the above-mentioned polyether polyols, a polyether polyol in which 95% by mass or more of the alkylene oxide added to the initiator is propylene oxide is preferably used. Further, the hydroxyl value of the polyether polyol effectively used in the present invention is preferably in the range of 30 to 300 mgKOH / g, and particularly preferably in the range of 32 to 290 mgKOH. Such a polyether polyol can be used alone or in combination as appropriate as long as it falls within the above range of hydroxyl value.

In particular, the polyether polyol preferably used in the present invention does not use an amine compound as an initiator. That is, a polyether polyol obtained by using a compound having two or more active hydrogen groups, which is different from the amine compound, and adding a predetermined amount of propylene glycol to the compound is advantageously used. .. Specific examples of such a polyether polyol include polypropylene glycol using propylene glycol as an initiator, polypropylene glycol using glycerin as an initiator, polypropylene glycol using bisphenol A as an initiator, and the like. In other words, polypropylene glycol obtained by adding propylene oxide to a polyhydric alcohol such as propylene glycol, glycerin, or bisphenol A as an initiator is preferably used. When a polyether polyol obtained by using an amine compound is used as an initiator, it is regulated so as to be 5% by mass or less of the polyol compound, and more preferably 1% by mass or less. It is regulated to be a ratio. This is because when an amine compound is used as an initiator, it is easily diluted with water and the risk of water turbidity is caused.

The above-mentioned polyether polyol generally has a molecular weight of about 200 to 4000, more preferably about 250 to 3200, and particularly preferably about 300 to 2000. It is even more desirable to have a molecular weight. If the molecular weight is smaller than 200, it is easily diluted with water, which may cause cloudiness or outflow, and if the molecular weight is larger than 4000, the viscosity of the liquid A may increase or the solidification strength may decrease. There is.

(Second active hydrogen group-containing compound)
Further, in the present invention, as the active hydrogen group-containing compound, the second active hydrogen group-containing compound used in combination with the above-mentioned first active hydrogen group-containing compound is such a first active hydrogen group-containing compound. Those having a faster reaction rate than the polyol compound will be used. Specifically, the viscosity of a solution in which polyisocyanate and dioctyl phthalate are mixed at a volume ratio of 1: 1 is measured in advance without containing a catalyst, and then a second solution is added to the solution. The active hydrogen group-containing compound was added so as to have a content ratio of 0.5% by mass, the viscosity of the solution 1 minute after the addition was measured, and the viscosity of the solution before and after the addition of the second active hydrogen group-containing compound was measured. Those having a viscosity increase rate of 1.5 times or more, preferably 1.5 to 50 times, more preferably 2 to 45 times, still more preferably 4 to 40 times the viscosity before addition are used. .. If the measured value of the solution viscosity 1 minute after such addition is less than 1.5 times the solution viscosity before addition, the chemical composition is diluted with water, causing white turbidity of water or water. There is a possibility that the problem of the outflow of the chemical solution to the drug solution may occur, and if the rate of increase in the viscosity of the solution 1 minute after the addition becomes too high, it causes difficulty in injecting the chemical solution, etc., and causes a problem in the injection workability. ..

By the way, without using the second active hydrogen group-containing compound in combination, the polyol compound which is the first active hydrogen group-containing compound described above is used alone, and it (liquid A) and polyisocyanate (liquid B) are combined. When these two liquids are mixed, the two liquids react and hardening progresses, but since the increase in viscosity due to the hardening is gradual, when the chemical liquid composition is injected into the ground where spring water flows, it is mixed. Since the resulting chemical composition is injected into the ground faster than it reacts, it is washed away by spring water and diluted, resulting in white turbidity of water or outflow of the chemical composition into water. May be aroused. On the other hand, when the solution A containing only the above-mentioned second active hydrogen group-containing compound and the solution B containing polyisocyanate are mixed without using the first active hydrogen group-containing compound in combination, the curing rate is high. It may become too fast and cure may begin before it is mixed and then injected into the ground where the spring water flows, making it difficult to inject sufficient chemicals.

Therefore, in the present invention, as the active hydrogen group-containing compound, a liquid A containing 90% by mass or more of the above-mentioned first active hydrogen group-containing compound and the above-mentioned specific second active hydrogen group-containing compound is used. In addition to the use, by adopting a configuration in which such liquid A and liquid B are adjusted within a predetermined viscosity range, low viscosity is maintained until the liquid A and liquid B are mixed with a mixer. By maintaining it, while ensuring excellent injection workability, by appropriately thickening after mixing, a reactant that is difficult to be diluted in spring water is formed, and it becomes cloudy in water and spring water of chemical composition. The elution of hydrogen is effectively prevented.

The second active hydrogen group-containing compound is contained in the total active hydrogen group-containing compound in a proportion of 10% by mass or less, preferably 8% by mass or less, and more preferably 5% by mass or less. It will be. If the content of the second active hydrogen group-containing compound is more than 10% by mass, the reaction may become too fast and the mixture of the liquid A and the liquid B may be deteriorated. Further, if the content of the second active hydrogen group-containing compound becomes too small, the reaction does not proceed sufficiently and is easily washed away by the spring water, which may cause the chemical solution to flow out or the water to become cloudy. It is preferably contained in a proportion of 0.1% by mass or more, preferably 0.2% by mass or more. In particular, the second active hydrogen group-containing compound is 0.1% by mass or more and less than 2% by mass, preferably 0.1 to 1.8% by mass, particularly 0.2 to 1.5% by mass in the liquid A. It is desirable that it is contained so as to have a ratio of%.

Examples of the second active hydrogen group-containing compound used in the present invention include amine compounds containing a primary amino group and / or a secondary amino group, preferably an aliphatic amine compound. Specifically, it is an aliphatic amine compound such as ethylenediamine, hexanediamine, octanediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc., and aminoethylpiperazin, polyethyleneimine, dimerate polyamideamine, etc. Polyamide amine and the like can also be preferably used. These second active hydrogen group-containing compounds may be used alone or in combination of two or more.

In addition, in the present invention, in addition to the above-mentioned first and second active hydrogen-containing compounds, various known compounds having other active hydrogen groups are used as the third active hydrogen group-containing compound. It is possible. Examples of such compounds include amines, thiols, carboxylic acids, silanol group-containing compounds, and active methylene group-containing compounds. Further, among such compounds, it is desirable to use a compound having two or more active hydrogen groups capable of reacting with polyisocyanate in the molecule, and a compound having a molecular weight of about 250 to 3000 is preferably used. ..

By the way, in the present invention, it is also effective to further add a catalyst to the solution A. As the catalyst used there, at least one of a known metal catalyst and a tertiary amine catalyst can be selected, and among them, it is more preferable to use both a metal catalyst and a tertiary amine catalyst in combination. preferable. The content of the metal catalyst is preferably about 0.1 to 5 parts by mass, preferably about 0.5 to 2.5 parts by mass, based on 100 parts by mass of the entire active hydrogen group-containing compound. The tertiary amine catalyst is contained in an amount of about 0.1 to 5 parts by mass, preferably about 0.5 to 2.5 parts by mass, based on 100 parts by mass of the entire active hydrogen group-containing compound. Become. If the amount of these catalysts added is less than 0.1 parts by mass, the contribution to the reaction is reduced and the strength development is delayed, while if it is more than 5 parts by mass, the reaction becomes too fast. There is a problem that it becomes difficult to control the reaction rate. In addition, by using the metal catalyst and the tertiary amine catalyst in combination, the reaction between the liquid A and the liquid B immediately occurs regardless of whether the chemical composition is simply mixed or when it comes into contact with spring water. A reaction product that is evoked and has the necessary and sufficient strength can be formed.

(Metal catalyst)
In the present invention, the metal catalyst as described above can be selected and used without particular limitation from known ones. For example, organic acid metal salts such as sodium, potassium, calcium, tin, lead, bismuth, zinc, iron, nickel, zirconium, and cobalt, and organic metal complexes can be used. Among them, examples of the organic acid metal salt include salts of acetic acid, octyl acid, neodecanoic acid, naphthenic acid, loginic acid and the like with the above metal, and examples of the organic metal complex include a complex of acetylacetone and the like with the above metal. Can be mentioned. 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 dilaurylate; acetylacetone iron, acetylacetone zinc, acetylacetone zirconium, acetylacetone nickel, acetylacetone tin and the like. These metal salts and metal complexes may be used as those dissolved in a diluent such as mineral spirits, organic acids, glycols and esters in order to improve their handleability. Further, these metal catalysts may be used alone or in combination of two or more. Among these, preferred examples include acetates of potassium, tin, lead, bismuth or zinc, octylate, neodecanoate, laurylate, and acetylacetone complexes, and more preferably catalysts using potassium as a metal. , Will be preferably used.

(3rd grade amine catalyst)
Further, the tertiary amine catalyst is a foaming catalyst having an action of promoting the reaction between the isocyanate component and water when foaming is intended by contact with external water, and the reaction between the isocyanate component and the polyol component. There are resinification catalysts having an action of promoting, and isocyanurate-forming catalysts having an action of promoting the trimerization of isocyanate components, all of which are appropriately selected from known ones. ..

Specifically, as the foaming catalyst, N, N, N', N ", N" -pentamethyldiethylenetriamine, N, N, N'-triethylaminoethylethanolamine, bis (dimethylaminoethyl) ether, N , N, N'-trimethylaminoethylpiperazine, N, N-dimethylaminoethoxyethanol, triethylamine and the like. 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-methylmorpholin, 1 -Methylimidazole, 1,2-dimethylimidazole and the like can be mentioned. Further, examples of the isocyanurate-forming catalyst include 2,4,6-tris (dimethylaminomethyl) phenol, N, N', N "-tris (dimethylaminopropyl) -hexahydro-s-triazine and the like. The catalyst may be used alone or in combination of two or more, and among these, a resinification catalyst or a trimerization catalyst is preferably used.

<Liquid B>
(Polyisocyanate)
On the other hand, the liquid B, which is one of the other two liquids constituting the chemical liquid composition for ground injection according to the present invention, is prepared by using polyisocyanate as an essential component as in the conventional case. In the present invention, the content of polyisocyanate in such solution B is adjusted to be 70 to 100% by mass, preferably 80 to 100% by mass, and more preferably 90 to 100% by mass. Is desirable. If the content of such polyisocyanate is less than 70% by mass, there is a problem that the strength of the reaction product is lowered. Therefore, it is desirable that the proportion of polyisocyanate in the liquid B is high, and there is no problem even if the liquid B is formed only with the polyisocyanate.

Further, in the present invention, the polyisocyanate which is an essential component of the liquid B is an organic isocyanate compound having two or more isocyanate groups (NCO groups) in the molecule, for example, diphenylmethane diisocyanate (MDI), poly. Aromatic polyisocyanate such as methylene polyphenylene polyisocyanate (crude MDI), tolylene diisocyanate, polytolylen polyisocyanate, xylylene diisocyanate, naphthalene diisocyanate, aliphatic polyisocyanate such as hexamethylene diisocyanate, alicyclic poly such as isophorone diisocyanate. In addition to isocyanates, urethane prepolymers having an isocyanate group at the molecular terminal, isocyanurate-modified polyisocyanates, carbodiimide-modified products and the like can be mentioned. These polyisocyanate components may be used alone or in combination of two or more. In general, MDI and crude MDI are preferably used from the viewpoints of reactivity, economy, handleability and the like.

(Form of reaction)
Then, in the present invention, the first active hydrogen group-containing compound and the second active hydrogen group-containing compound, which are essential components constituting the active hydrogen group-containing compound which is the main component in the liquid A, are in the liquid B. It will be reacted with polyisocyanate in parallel, but immediately after mixing the solutions A and B, due to the difference in reaction rate, between the second active hydrogen group-containing compound and the polyisocyanate. The reaction occurs preferentially, and in the latter half of the reaction, the first active hydrogen group-containing compound reacts with the polyisocyanate. In particular, when the second active hydrogen group-containing compound satisfies the conditions of the present invention, the mixture exhibits a thickening behavior immediately after injection without a significant change in curing time due to such a sequential reaction form, and water. By forming a reaction product that is difficult to dilute with water, it becomes difficult to be mixed with water, and cloudiness can be advantageously prevented.

It is preferable that the above-mentioned solution A and / or solution B, which constitutes the chemical composition according to the present invention, contains a flame retardant depending on the purpose of use. When this flame retardant is added to the liquid A, the ratio is about 5 to 50 parts by mass, preferably about 10 to 30 parts by mass with respect to 100 parts by mass of the total active hydrogen group-containing compound. It is desirable to be used. When added to the liquid B, it may be used in a proportion of about 5 to 40 parts by mass, preferably about 10 to 30 parts by mass with respect to 100 parts by mass of the polyisocyanate. desirable.

Specific examples of such flame retardants include brominated flame retardants, chlorine flame retardants, phosphorus flame retardants, halogenated phosphoric acid esters, and inorganic flame retardants. These may be used alone, or two or more kinds may be used in combination. Among these, a phosphoric acid ester and a halide phosphoric acid ester are preferably used because they have a small burden on the environment and also function as a thickener for the effervescent composition. Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, and trixylenyl phosphate. Examples of the halide phosphate include tris (chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (dichloropropyl) phosphate, tetrakis (2-chloroethyl) dichloroisopentyldiphosphate, and polyoxyalkylene bis. (Dichloroalkyl) phosphate and the like can be mentioned.

In the present invention, it is desirable that the above-mentioned solutions A and B do not substantially contain a foaming agent, and therefore are not positively present in the reaction system. Here, the fact that the foaming agent is substantially not blended means that when the foaming agent is other than water, the content of the foaming agent is less than 1 ppm by quantitative analysis, and a trace amount of foaming agent of less than 1 ppm is used. Even if is detected, it is regarded as a foreign substance and it is judged that the foaming agent is not added. The quantitative analysis will be performed using gas chromatography, liquid chromatography, or the like. When the foaming agent is water, water is intentionally added to the chemical composition separately from the water contained in each active hydrogen group-containing compound, polyisocyanate, catalyst, and other additives to be blended. It means that it is not added to the substance. Specifically, if the abundance of water in the liquid A or the liquid B is less than 0.1% by mass, it is regarded as a foreign substance, and it is determined that the foaming agent is not blended.

It is possible to appropriately add various additives similar to the conventional ones to each of the above-mentioned solutions A and B, which constitute the chemical composition according to the present invention, according to the purpose of use thereof. .. For example, as an additive to the liquid A or the liquid B, a foam stabilizer, a thickener and the like can be mentioned. These additives are used in a ratio of about 0.1 to 3 parts by mass, preferably about 0.3 to 1 part by mass, based on 100 parts by mass of the total active hydrogen group-containing compound constituting the liquid A. It becomes. The liquid B is used so as to have a ratio of about 0.1 to 3 parts by mass, preferably about 0.3 to 2 parts by mass, with respect to 100 parts by mass of the polyisocyanate constituting the liquid B. It becomes.

Among these additives, the defoaming agent is used to uniformly adjust the cell structure of the foam formed by the reaction of the liquid A and the liquid B. Examples of this defoaming agent include silicone, nonionic surfactant, polyoxyalkylene-modified dimethylpolysiloxane, polysiloxaneoxyalkylene copolymer, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, and lauryl fatty acid ethylene oxide. Additives and the like are mentioned, and among these, silicone and nonionic surfactant are preferably used. These may be used alone or in combination of two or more. Further, among the defoaming agents, silicone-based defoaming agents are more preferable, and polyoxyalkylene-modified dimethylpolysiloxane, polysiloxane oxyalkylene copolymer, and the like are preferable.

In addition, the thickener is used as a solvent, is dissolved in the liquid A or the liquid B, and has a function of reducing the thickness of those liquids, and particularly as long as it has such a function. Not limited to, for example, alcohols such as methanol and ethanol, ethers such as ethyl cellsolve and butyl cellsolve, cyclic esters such as propylene carbonate, esters such as dicarboxylic acid methyl ester and ethylene glycol monomethyl ether acetate. Classes, petroleum hydrocarbons and the like. These may be used alone or in combination of two or more.

By the way, each of the solutions A and B prepared according to the present invention is adjusted so that the viscosity at a temperature of 25 ° C. is 50 to 500 mPa · s, preferably 100 to 400 mPa · s. There is a need. If this viscosity is higher than 500 mPa · s, the liquid A and the liquid B become viscous liquids, and the fluidity at the time of pumping is poor, which may cause an increase in the injection pressure and deteriorate the injection workability. Further, when their viscosities are lower than 50 mPa · s, the chemical solution is easily diluted with water, which may cause problems such as cloudiness of wastewater.

In addition, when using a chemical solution composition for ground injection according to the present invention, which is composed of solutions A and B as described above, both solutions are mixed at the time of use, and the target ground, rock, etc. are treated. The foundation is formed by being introduced by injection or pouring and being reaction-cured. The mixing ratio (A: B) of the liquid A and the liquid B that gives the desired chemical composition can be appropriately changed depending on the hydroxyl group content in the liquid A and the NCO group content in the liquid B. However, in general, it is adopted in the range of A: B = 1: 0.5 to 1: 3, preferably 1: 1 to 1: 2.5 on a volume basis. Further, the method of using the liquids A and B is not particularly limited as long as the two liquids can be surely mixed immediately before their use (injection). The injection method and the pouring method can be appropriately adopted.

Then, when the liquid A and the liquid B are mixed, the chemical liquid composition according to the present invention is advantageously configured so that the foaming ratio is 1 to 15 times. In particular, when it is used when injecting into the ground where spring water comes out, the foaming ratio is 1 to 2 times, preferably 1 to 1.5 times, more preferably 1 to 2 times, without substantially adding a foaming agent. It is desirable to set it to be 1 to 1.3 times. When liquid A and liquid B are mixed and injected into water or the ground in the presence of water, the foaming ratio is usually 2 to 15 times, preferably 3 to 15 times when it comes into contact with external water serving as a foaming agent. The foaming ratio is appropriately adjusted according to the purpose so as to have a foaming ratio of 10 times.

As a result, in the chemical composition injected into the ground with spring water, the foaming ratio is suppressed to 2 times or less in the part that does not come into contact with water, while the part that comes into contact with water is about 2 times. A partial or gradual foaming form of foaming at a higher foaming ratio is realized. The reaction product injected into the ground at this time gives a high-strength curing reaction product having a low foaming ratio to the portion not in contact with water on the inner side, while the foaming ratio of the portion in contact with water on the outer side is high. Since it becomes a form, it is possible to advantageously realize the strength that sufficiently supports the water pressure of the spring water.

Hereinafter, the present invention will be clarified more specifically by showing some examples and comparative examples of the present invention, but the present invention is subject to any restrictions by the description of such examples. It goes without saying that it is not a thing. Further, in addition to the following examples, various modifications and modifications to the present invention are made based on the knowledge of those skilled in the art, as long as the gist of the present invention is not deviated from the specific description described above. It should be understood that improvements can be made.

When the liquid A and the liquid B were mixed and cured by the reaction together with the viscosity of the second active hydrogen group-containing compound in the thickening test and the viscosities of the liquid A and the liquid B obtained in Examples and Comparative Examples. The foaming ratio and curing time of the reaction product, the light transmittance of water after reaction and foaming in water, and the amount of chemical liquid outflow after foaming in water are measured according to the following methods. Or evaluated. In addition, both "%" and "part" shown below are based on mass.

(1) Viscosity The additive-free viscosity and the viscosity after 1 minute in the thickening test of the second active hydrogen group-containing compound, and the viscosities of the solutions A and B obtained in Examples and Comparative Examples are determined by JIS-K, respectively. According to -7117-1, measurement was performed at a temperature of 25 ° C. using a B-type viscosity measuring device.

(2) Foaming Magnification Liquid A and liquid B adjusted to a temperature of 25 ° C. are weighed at a predetermined mixing ratio shown in Table 2 or Table 3 below so that the total volume is 100 ml, and weighed them. After the liquid was contained in a 2 L disk cup, it was thoroughly mixed and stirred to cure it. Then, the foaming height of the reaction product after the completion of the curing reaction was measured, and the foaming ratio was determined.

(3) Curing time After mixing the liquid A and the liquid B adjusted to a temperature of 25 ° C. at the mixing ratio shown in Table 2 or Table 3, gas is generated from the reaction product and the foaming height is increased. The time when the reaction product did not change or the time when the reaction product was skewered and did not stick to the inside was measured, and the later one was defined as the end point of the curing time.

(4) White turbidity test in running water (light transmittance)
Liquid A and liquid B adjusted to a temperature of 25 ° C. are weighed and mixed at the mixing ratio shown in Table 2 or Table 3 so that the total volume is 100 ml. Immediately after the mixing, a mixture of liquids A and B is poured into 1 L of water at 20 ° C. contained in a 2 L disc cup while stirring at 1000 rpm with a homodisper, and foaming starts. Stir in water until Then, after the start of foaming, the stirring blade was removed and the mixture was allowed to stand until the reaction subsided. Then, after the reaction was completed, the light transmittance at a wavelength of 500 nm was measured using a spectrophotometer (U-2800 type spectrophotometer manufactured by Hitachi High-Technologies Corporation). When the transmittance was less than 70%, it was evaluated that the water became cloudy.

(5) Amount of chemical liquid outflow A mesh net is attached to the lower opening of a cylindrical shape having a diameter of 50 mm and a length of 250 mm, and a lid is closed from the outside to close the cylinder. After stuffing so that it became, then 200 ml of water was poured. Then, 20 g of the chemical solution mixed at the mixing ratio shown in Table 2 or Table 3 is mixed and immediately poured from the upper opening of the cylindrical shape, and then the lower lid of the cylindrical shape is removed, and then the upper opening is opened. A more piston-shaped stick was pushed in to push the water in the mold out of the mesh net. Then, the extruded water was collected, and the weight of the chemical solution extruded together with the water was calculated.

(6) Injection pressure test After adjusting the temperatures of solutions A and B to 10 ° C., the injection pressure when injected into an injection tube having an inner diameter of 12 mm and a length of 20 m was measured using an injection machine. Then, those having an injection pressure of 2.5 MPa or less were regarded as acceptable.

-Thickening test of the second active hydrogen group-containing compound-
Using 307 parts of Polyisocyanate manufactured by Manka Kagaku Japan Co., Ltd .: Wannate PM-200 (viscosity: 160 mPa · s / 25 ° C., Polymeric MDI) and 245 parts of dioctyl phthalate (DOP) manufactured by Tokyo Kasei Kogyo Co., Ltd. After mixing them (volume ratio 1: 1) and measuring the viscosity of the obtained mixed solution, 2.8 parts (2.8 parts) of various second active hydrogen group-containing compounds shown in Table 1 below ( 0.5% of the mixed solution) was added to the mixed solution, and the viscosity 1 minute after the mixing was measured. Then, the viscosity thickening ratio of the viscosity 1 minute after the addition with respect to the viscosity before the addition of the second active hydrogen group-containing compound to the mixed solution was calculated and shown in Table 1 below. Here, those having such a thickening ratio of 1.5 times or more are accepted.

(Example 1)
-Preparation of solution A-
As the first active hydrogen group-containing compound polyol compound, a polyether polyol manufactured by Sanyo Kasei Kogyo Co., Ltd .: PP-400 [Initiator: propylene glycol, alkylene oxide: propylene oxide (PO) 100% by mass, molecular weight: 400, functional 40 parts of group number: 2, hydroxyl value: 280 mgKOH / g] and a polyether polyol manufactured by Sanyo Kasei Kogyo Co., Ltd .: PP-1000 (starter: propylene glycol, PO: 100% by mass, molecular weight: 1000, number of functional groups: 2) 30 parts of hydroxyl value: 112 mgKOH / g) and a polyether polyol manufactured by Sanyo Kasei Kogyo Co., Ltd .: GP-3000 (starter: glycerin, PO: 100% by mass, molecular weight: 3000, number of functional groups: 3, hydroxyl value: 30 parts of 56 mgKOH / g) is used, and as a second active hydrogen group-containing compound, a part of PEHA (pentaethylenehexamine, primary and secondary amino groups: 6) manufactured by Toso Co., Ltd., and a metal As a catalyst, 0.8 part of Pucat 15G (potassium catalyst: potassium octylate) manufactured by Nippon Kagaku Sangyo Co., Ltd., and as a tertiary amine catalyst, Kaorizer No. Add 0.8 parts of 31 (resinization catalyst: dipropylene glycol solution of 33% triethylenediamine) and 30 parts of TMCPP [Tris (chloropropyl) phosphate] manufactured by Daihachi Chemical Industry Co., Ltd. as a flame retardant. Solution A was obtained by mixing uniformly. Then, the viscosity of the obtained solution A was measured, and the results are shown in Table 2 below.

-Preparation of solution B-
Wannate PM-200 (Polymeric MDI) manufactured by Manka Kagaku Japan Co., Ltd. was used as the polyisocyanate, and 100 parts thereof was prepared as liquid B. Then, the viscosity of the prepared liquid B was measured, and the results are shown in Table 2 below.

-Reaction of liquid A and liquid B-
Liquid A and liquid B obtained above are combined at a volume ratio of 1: 1 and uniformly mixed at room temperature to react, and then various evaluation tests are performed according to the above-mentioned evaluation method. The results are shown in Table 2 below.

(Examples 2 to 3)
In Example 1, the test was carried out according to the same method as in Example 1 except that the second active hydrogen group-containing compound was divided into 2 parts or 5 parts, respectively. The results obtained are shown in Table 2 below.

(Example 4)
In Example 1, the same method as in Example 1 except that the second active hydrogen group-containing compound was replaced with TEPA (tetraethylenepentamine, primary and secondary amino groups: 5) manufactured by Tosoh Corporation. Each test was conducted according to the above. The results obtained are shown in Table 2 below.

(Example 5)
In Example 1, the same method as in Example 1 was followed except that the second active hydrogen group-containing compound was replaced with TETA (triethylenetetramine, primary and secondary amino groups: 4) manufactured by Tosoh Corporation. , Each test was conducted. The results obtained are shown in Table 2 below.

(Example 6)
In Example 1, the second active hydrogen group-containing compound was replaced with L-2513 (modified polyamide amine, primary and secondary amino groups: average 3 to 5) manufactured by Sanyo Chemical Industries, Ltd. Each test was performed according to the same method as in Example 1. The results obtained are shown in Table 2 below.

(Example 7)
As the first active hydrogen group-containing compound polyol compound, a polyether polyol manufactured by Sanyo Kasei Kogyo Co., Ltd .: PP-400 [Initiator: propylene glycol, alkylene oxide: propylene oxide (PO) 100% by mass, molecular weight: 400, functional 40 parts of group number: 2, hydroxyl value: 280 mgKOH / g] and a polyether polyol manufactured by Sanyo Kasei Kogyo Co., Ltd .: PP-1000 (starter: propylene glycol, PO: 100% by mass, molecular weight: 1000, number of functional groups: 2) 30 parts of hydroxyl value: 112 mgKOH / g) and a polyether polyol manufactured by Sanyo Kasei Kogyo Co., Ltd .: GP-3000 (starter: glycerin, PO: 100% by mass, molecular weight: 3000, number of functional groups: 3, hydroxyl value: 30 parts of 56 mgKOH / g) is used, and as a second active hydrogen group-containing compound, aminoethyl piperazine manufactured by Tokyo Kasei Kogyo Co., Ltd. [N- (2-aminoethyl) piperazine [N- (2-aminoethyl) piperazine, primary and secondary Amino group number: 2], 0.8 part of Pucat 15G (potassium catalyst: potassium octylate) manufactured by Nippon Kagaku Sangyo Co., Ltd. as a metal catalyst, and Kaorizer No. 1 manufactured by Kao Co., Ltd. as a tertiary amine catalyst. Add 0.8 parts of 31 (resinization catalyst: dipropylene glycol solution of 33% triethylenediamine) and 30 parts of TMCPP [Tris (chloropropyl) phosphate] manufactured by Daihachi Chemical Industry Co., Ltd. as a flame retardant. Solution A was obtained by uniformly mixing. Then, the viscosity of the obtained solution A was measured, and the results are shown in Table 2 below.

In addition, Wannate PM-200 (Polymeric MDI) manufactured by Manka Kagaku Japan Co., Ltd. was used as the polyisocyanate, and 100 parts thereof was prepared as the B solution. Then, the viscosity of the prepared liquid B was measured, and the results are shown in Table 2 below.

Then, the liquid A and the liquid B obtained above are combined at a volume ratio of 1: 1 and uniformly mixed at room temperature to react, and then various types are followed according to the above-mentioned evaluation method. Evaluation tests were performed and the results are shown in Table 2 below.

(Example 8)
In Example 7, each test was carried out according to the same method as in Example 7 except that the second active hydrogen group-containing compound was replaced with ethylenediamine (primary amino group number: 2) manufactured by Tokyo Chemical Industry Co., Ltd. rice field. The results obtained are shown in Table 2 below.

(Example 9)
In Example 7, the same as in Example 7 except that the second active hydrogen group-containing compound was replaced with hexanediamine (1,6-hexanediamine, primary amino group number: 2) manufactured by Tokyo Chemical Industry Co., Ltd. Each test was conducted according to the method of. The results obtained are shown in Table 2 below.

(Example 10)
In Example 1, each test was carried out according to the same method as in Example 1 except that the polyisocyanate was replaced with Wannate PM-130 (Polymeric MDI) manufactured by Manka Kagaku Japan Co., Ltd. The results obtained are shown in Table 2 below.

(Comparative Example 1)
Example 7 and Example 7 except that the second active hydrogen group-containing compound was replaced with diethyltoluenediamine (3,5-diethyltoluenediamine, primary amino group number: 2) manufactured by Lonza Japan Co., Ltd. Each test was conducted according to the same method. The results obtained are shown in Table 3 below.

(Comparative Example 2)
In Example 7, the same method as in Example 7 was followed except that the second active hydrogen group-containing compound was replaced with D2000 (polyetheramine, primary amino group number: 2) manufactured by Mitsui Kagaku Fine Co., Ltd. Each test was conducted. The results obtained are shown in Table 3 below.

(Comparative Example 3)
In Example 7, each test was carried out according to the same method as in Example 7 except that the second active hydrogen group-containing compound was replaced with diethanolamine (secondary amino group number: 1) manufactured by Tokyo Chemical Industry Co., Ltd. rice field. The results obtained are shown in Table 3 below.

(Comparative Example 4)
In Example 7, each test was carried out according to the same method as in Example 7 except that the second active hydrogen group-containing compound was replaced with triethanolamine (number of tertiary amino groups: 1) manufactured by Tokyo Chemical Industry Co., Ltd. Was done. The results obtained are shown in Table 3 below.

(Comparative Example 5)
In Example 7, each test was carried out according to the same method as in Example 7 except that the second active hydrogen group-containing compound was replaced with PP-400. The results obtained are shown in Table 3 below.

(Comparative Example 6)
In Example 7, the second active hydrogen group-containing compound was 750ED manufactured by Sanyo Kasei Kogyo Co., Ltd. (initiator: ethylenediamine, PO: 100% by mass, molecular weight: 300, number of functional groups: 4, hydroxyl value: 750 mgKOH / g, The tests were carried out according to the same method as in Example 7 except that the primary and secondary amino groups were replaced with 0). The results obtained are shown in Table 3 below.

(Comparative Example 7)
In Example 7, each test was carried out according to the same method as in Example 7 except that the second active hydrogen group-containing compound was not added. The results obtained are shown in Table 3 below.

(Comparative Example 8)
As the first active hydrogen group-containing compound polyol compound, a polyether polyol manufactured by Asahi Denka Kogyo Co., Ltd .: BPX-2000 [Initiator: bisphenol A, alkylene oxide: propylene oxide (PO) 100% by mass, molecular weight: 2000, functional 70 parts of group number: 2, hydroxyl value: 56 mgKOH / g] and a polyether polyol manufactured by Sanyo Kasei Kogyo Co., Ltd .: GP-3000 (starter: glycerin, PO: 100% by mass, molecular weight: 3000, number of functional groups: 3, Pcat 15G (potassium catalyst: potassium octylate) manufactured by Nippon Kagaku Sangyo Co., Ltd. was used as a metal catalyst using 30 parts of hydroxyl value: 56 mgKOH / g) without adding a second active hydrogen group-containing compound. ), As a tertiary amine catalyst, Kaorizer No. 1 manufactured by Kao Co., Ltd. Solution A was obtained by adding 1.2 parts of 31 (resinification catalyst: dipropylene glycol solution of 33% triethylenediamine) and mixing them uniformly. Then, the viscosity of the obtained solution A was measured, and the results are shown in Table 3 below.

In addition, Wannate PM-200 (Polymeric MDI) manufactured by Manka Kagaku Japan Co., Ltd. was used as the polyisocyanate, and 100 parts thereof was prepared as the B solution. Then, the viscosity of the prepared liquid B was measured, and the results are shown in Table 3 below.

Then, the liquid A and the liquid B obtained above are combined at a volume ratio of 1: 1 and uniformly mixed at room temperature to react, and then various types are followed according to the above-mentioned evaluation method. Evaluation tests were performed and the results are shown in Table 3 below.

As is clear from the results shown in Tables 2 and 3, the second active hydrogen group-containing compound having a thickening ratio of 1.5 times or more in the thickening test in Table 1 is contained as a component of the liquid A. In the chemical liquid composition composed of the combination of the liquid A and the liquid B according to Examples 1 to 10, the light transmittance was 70% in the measurement of the light transmittance at a wavelength of 500 nm after the reaction curing operation in water. As a result, no whitening of water was observed. In addition, since the outflow of the chemical solution to the water was hardly confirmed in the measurement of the amount of the chemical solution outflow, it is diluted with the spring water even when the chemical solution composition is injected into the ground where there is a large amount of spring water. It was found that the deterioration of the physical characteristics of the curing reaction product was effectively prevented, and that the injected chemical composition was not flushed with the spring water, and the problem causing water pollution could be prevented.

On the other hand, the liquid A according to Comparative Examples 1 to 8 containing the second active hydrogen group-containing compound having a thickening ratio of less than 1.5 times in the thickening test in Table 1 as a component of the liquid A. In the combination of solution B and solution B, whitening of water was noticeably observed after the reaction curing operation in water, and the presence of the drug solution extruded together with water was also confirmed in the measurement of the amount of chemical solution outflow. It is predicted that the injected chemical composition will also flow due to the flow of spring water, making it impossible to stop the water sufficiently, and that the chemical composition poured into the spring will cause water pollution. rice field.

Claims (10)

In a chemical solution composition for ground injection, which comprises a solution A containing an active hydrogen group-containing compound as a main component and a solution B containing a polyisocyanate as a main component.
The active hydrogen group-containing compound contains a first active hydrogen group-containing compound composed of a polyol compound having a hydroxyl group in a proportion of 90% by mass or more, and is more polyisocyanate than the first active hydrogen group-containing compound. together containing at least a fast second active hydrogen group-containing compound reaction rate for consuming a second active hydrogen group-containing compound is, in the state without the addition of catalyst, a polyisocyanate and dioctyl phthalate in a volume ratio of 1: 1 When added to the mixed solution at a content of 0.5% by mass, the increase in the viscosity of the solution 1 minute after the addition is 1.5 times the viscosity of the solution before the addition. The above, and the second active hydrogen group-containing compound is contained in the liquid A at a ratio of 0.1% by mass or more and less than 2% by mass, and the liquid A and the liquid B are contained. A chemical composition for ground injection, which has a viscosity at 25 ° C. of 50 to 500 mPa · s, respectively.
The polyol compound contains a polyether polyol obtained by adding an alkylene oxide to the initiator in a proportion of 90% by mass or more, and 95% by mass or more of the alkylene oxide added to the initiator is propylene oxide. The chemical composition for ground injection according to claim 1, wherein the polyether polyol has a hydroxyl value of 30 to 300 mgKOH / g. The chemical composition for ground injection according to claim 2, wherein the initiator is a polyhydric alcohol. The chemical composition for ground injection according to claim 2 or 3, wherein the polyether polyol has a molecular weight of 200 to 4000. The invention according to any one of claims 1 to 4, wherein the content ratio of the polyol obtained by using the amine compound as the initiator in the polyol compound is 5% by mass or less. Chemical composition for ground injection. The ground injection according to any one of claims 1 to 5, wherein the second active hydrogen group-containing compound is an amine compound having a primary amino group and / or a secondary amino group. Medicinal solution composition. Any of claims 1 to 6, wherein the second active hydrogen group-containing compound is contained in a proportion of 0.1 to 8% by mass of the total active hydrogen group-containing compound. The chemical composition for ground injection according to item 1. The chemical solution for ground injection according to any one of claims 1 to 7, wherein the solution A further contains at least one of a metal catalyst and a tertiary amine catalyst. Composition. The chemical composition for ground injection according to any one of claims 1 to 8, wherein the curing reaction product has a foaming ratio of 2 times or less. The ground according to any one of claims 1 to 9, wherein the mixing ratio of the liquid A and the liquid B is 1: 0.5 to 1: 3 on a volume basis. Chemical composition for injection.