JP2019001838A - Agent liquid composition for grouting - Google Patents

Abstract

To provide an agent liquid composition for grouting, achieving sufficient strength capable of cutting off a large amount of water leakage or sump water, effectively inhibiting generation of white turbidness of water when contacted with water, and capable of suppressing expansion ration at low.SOLUTION: In an agent liquid composition for grouting consisting of an A liquid mainly containing polyol and a B liquid mainly containing polyisocyanate, the polyol is constituted that 95 mass% or more of alkylene oxide added to an initiator is propylene oxide, polyether polyol having hydroxyl group value of 30 to 300 mgKOH/g is contained at 90 mass% or more and the A liquid contains a metal catalyst.SELECTED DRAWING: None

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 ground where a large amount of water leakage or spring water is generated.

  Conventionally, injection of inorganic or organic grout is one of the countermeasures adopted for ground improvement applications for the stability and strengthening of unstable rocks and grounds, and for cavity filling applications that fill cracks and voids in artificial structures. There is a certain effect. For example, in Patent Document 1, as one of such grouts, an injectable liquid composition for stabilization such as a soil composed of a polyol and / or an organic polyamine compound, an organic polyisocyanate compound, and water is used. However, since the chemical composition disclosed in Patent Document 1 has a high foaming ratio of the foam as a whole, sufficient consolidation strength cannot be realized, and a large amount of water leakage or spring water is not achieved. There was a problem that it was difficult to completely stop water without obtaining the strength to support the water pressure.

  In addition, as a chemical solution composition intended to stop water against a large amount of water leakage or spring water, in Patent Document 2, a main agent containing an isocyanate component, a hardener containing castor oil-modified polyester polyol and a plasticizer component, and There has been proposed a water-stop agent for water-shielding sheets obtained by mixing. However, since this water-stopping agent has a low viscosity due to a large amount of plasticizer, when it is injected into the rock, the bleed-out plasticizer flows into the spring water, causing water pollution. Is inherent.

  Furthermore, when stopping a large amount of water leakage or spring water, there is a problem that some chemicals flow out together with the water leakage or spring water, thereby causing water turbidity and adversely affecting the environment. In addition, when the foaming ratio when the drug and water are in contact with each other increases, the volume of the foam that flows out along with water leakage and spring water also increases, and there is a problem that adverse effects on the environment increase.

Japanese Patent Laid-Open No. 7-26263 JP 2011-245453 A

  Here, the present invention has been made in the background of the circumstances as described above, and the problem to be solved is to realize a sufficient strength capable of stopping a large amount of water leakage and spring water. Another object of the present invention is to provide a chemical composition for ground injection which can effectively prevent water turbidity when it comes into contact with water and can suppress the foaming ratio to be small.

  And, in order to solve the above-mentioned problems, the present invention can be suitably implemented in various aspects as listed below, but each aspect described below is 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, but are understood based on the inventive concept grasped from the description of the entire specification. It should be.

(1) In a chemical composition for ground injection comprising A liquid mainly composed of polyol and B liquid mainly composed of polyisocyanate, 95 mass of alkylene oxide added to the initiator. % Or more is a polyether polyol having a hydroxyl value of 30 to 300 mg KOH / g in a proportion of 90% by mass or more, and the liquid A contains a metal catalyst. A chemical composition for ground injection characterized by the above.
(2) The chemical solution for ground injection according to the aspect (1), wherein the metal catalyst is contained at a ratio of 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyol. Composition.
(3) The chemical solution composition for ground injection according to the aspect (1) or the aspect (2), wherein the liquid A further contains a tertiary amine catalyst.
(4) The ground injection according to any one of the aspects (1) to (3), wherein a foaming agent is not substantially mixed in the liquid A and the liquid B. Chemical solution composition.
(5) The above-mentioned embodiment (2), wherein a curing reaction product having an expansion ratio of 2 times or less is provided.
1) thru | or the chemical | medical solution composition for ground injection as described in any one of the said aspect (4).
(6) The chemical composition for ground injection according to any one of the aspects (1) to (5), wherein the polyether polyol is obtained by adding an alkylene oxide to a polyhydric alcohol as an initiator. object.
(7) The aspect (1) to the above, characterized in that the content ratio of the polyether polyol obtained by using an amine compound as an initiator in the polyol is 5% by mass or less. The chemical composition for ground injection according to any one of aspects (6).
(8) The flame retardant is contained in at least one of the liquid A and the liquid B, and any one of the aspects (1) to (7) is characterized. Chemical solution composition for ground injection.
(9) The ground injection according to the aspect (8), wherein the flame retardant is contained in the liquid A at a ratio of 5 to 50 parts by mass with respect to 100 parts by mass of the polyol. Chemical solution composition.
(10) The aspect (8), wherein the flame retardant is contained in the liquid B at a ratio of 5 to 40 parts by mass with respect to 100 parts by mass of the polyisocyanate. A chemical composition for ground injection.
(11) The viscosity at 25 ° C. of the liquid A and the liquid B is 50 to 500 mPa · s, respectively, described in any one of the aspects (1) to (10) The medicinal solution composition for ground injection.
(12) Aspects (1) to (11) are characterized in that the A liquid and the B liquid are used in a ratio of 1: 0.5 to 1: 3 on a volume basis. The chemical composition for ground injection according to any one of the above.

And according to the structure of such a chemical | medical solution composition according to this invention, the various effects as enumerated below can be show | played.
(1) When injecting the chemical solution composition into the ground, even if it comes in contact with water, it can be applied advantageously without water becoming cloudy.
(2) Since the chemical solution composition is effectively prevented from being diluted and discharged, water contamination is prevented.
(3) By allowing the expansion ratio to be suppressed to 2 times or less, the injected chemical composition can suppress the foaming of the part not in contact with water, while the part in contact with water foams. A foamed form is realized, which can effectively secure the strength of the cured reaction product injected into the ground.
(4) By setting the expansion ratio to 2 times or less, it becomes difficult for the curing reaction product to flow into the water, which has an adverse effect on the environment due to the flow of the curing reaction product into the water. Will be prevented.

  In short, the present invention is a two-component chemical composition comprising a liquid A and a liquid B, and is obtained by adding a specific alkylene oxide to an initiator as a polyol as a main component of the liquid A. The ether polyol is used at a ratio of 90% by mass or more. And such specific polyether polyol was comprised so that 95 mass% or more of the alkylene oxide added to this initiator might be comprised with a propylene oxide, and a hydroxyl value might be 30-300 mgKOH / g. Is. Further, the liquid A further contains a metal catalyst together with the specific polyether polyol. Thus, a great feature exists when the intended purpose is achieved. And specifically, these A liquid and B liquid will be comprised as follows.

<Liquid A>
(Polyol)
In the liquid A which is one of the two liquids constituting the chemical composition for ground injection according to the present invention, 90% by mass or more of the polyol which is the main component constituting the liquid is an alkylene oxide with respect to a predetermined initiator. In such a specific polyether polyol, in order to effectively achieve the object of the present invention, 95% by mass or more of the alkylene oxide added to the initiator is added. It must be composed of propylene oxide. Moreover, the hydroxyl value of such a specific polyether polyol needs to be in the range of 30 to 300 mgKOH / g, and preferably in the range of 32 to 290 mgKOH / g. If the hydroxyl value is less than 30 mg KOH / g, the object of the present invention is hardly achieved. On the other hand, if it exceeds 300 mg KOH / g, problems such as water turbidity occur. Such specific polyether polyols can be used alone or in combination as appropriate as long as the above-mentioned regulations are satisfied.

  In addition, other known polyols are used in combination with the above-mentioned specific polyether polyols as polyols, and other known alkylenes such as ethylene oxide together with propylene oxide as alkylene oxides added to the initiator. Oxide can be used in combination, but if the content of the above-mentioned specific polyether polyol is less than 90% by mass or the addition amount of propylene oxide is less than 95% by mass, the present invention It will be difficult to achieve the objectives.

  By the way, the polyether polyol is generally a compound having at least two active hydrogen groups, for example, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol; amines such as ethylenediamine; A compound such as ethanolamine, diethanolamine or the like is used as an initiator, and is produced by an addition reaction or addition polymerization reaction comprising adding an alkylene oxide such as ethylene oxide or propylene oxide to the compound. .

  Among these, it is desirable that the specific polyether polyol used in the present invention does not use an amine compound as an initiator. When a polyether polyol obtained by using an amine compound as an initiator is used, it is desirable that the ratio is 5% by mass or less in the polyol, and it is more preferable. Is 1% by mass or less. In the present invention, a specific polyether polyol obtained by using an initiator that is not an amine compound and adding a predetermined amount of propylene glycol thereto is advantageously used. This is because if an amine compound is used as the initiator, it tends to be diluted with water and water turbidity may be caused. Examples of such a specific polyether polyol include polypropylene glycol using propylene glycol as an initiator, polypropylene glycol using glycerin as an initiator, and polypropylene glycol using bisphenol A as an initiator. That is, polypropylene glycol obtained by adding propylene oxide to a polyhydric alcohol such as propylene glycol, glycerin or bisphenol A as an initiator is desirably used.

  The specific polyether polyol as described above generally has a molecular weight of about 200 to 4000, more preferably about 250 to 3200, particularly 300 to 2000. It is more desirable to have a molecular weight of the order. If the molecular weight is less than 200, the compound is easily diluted with water, and may cause white turbidity. If the molecular weight is greater than 4000, it may be difficult to develop strength.

(Metal catalyst)
In the present invention, the liquid A further contains a metal catalyst together with the polyol having a specific polyether polyol content of 90% by mass or more as described above. Such a metal catalyst is generally about 0.1 to 5 parts by mass, preferably 0.2 to 3 parts by mass, more preferably 0.5 to 2.5 parts by mass with respect to 100 parts by mass of the polyol. It will be contained at a ratio. When the content of the metal catalyst is less than 0.1 parts by mass, there is a problem that the contribution to the reaction is small and the strength development is delayed. On the other hand, when the content exceeds 5 parts by mass, the reaction becomes too fast and the reaction The problem is that it becomes difficult to control the speed.

  In the present invention, any known metal catalyst can be used without any particular limitation, for example, organic acids such as sodium, potassium, calcium, tin, lead, bismuth, zinc, iron, nickel, zirconium, cobalt, etc. Metal salts and 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 organic metal complexes include complexes of acetylacetone and the like with the above metals. Is 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 dilaurate; acetylacetone iron, acetylacetone zinc, acetylacetonezirconium, acetylacetonenickel, acetylacetonetin and the like. These metal salts and metal complexes may be used as those dissolved in diluents such as mineral spirits, organic acids, glycols, and esters in order to improve the handleability. 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 complex are preferable, and catalysts using potassium as a metal are more preferable. It will be used suitably.

(Tertiary amine catalyst)
Moreover, in this invention, it is desirable to further contain a tertiary amine catalyst with the above-mentioned metal catalyst with respect to A liquid. The tertiary amine catalyst is generally in a proportion of 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight, more preferably 0.5 to 2.5 parts by weight with respect to 100 parts by weight of the polyol. In, it will be included. When the content of the tertiary amine catalyst is less than 0.1 parts by mass, there is a problem that the contribution to the reaction is small and the development of strength is slow, while when it is more than 5 parts by mass, the reaction becomes too fast, It becomes difficult to control the reaction rate.

  And as such a tertiary amine catalyst, when foaming is intended by contact with external water, a foaming catalyst having an action of promoting the reaction between polyisocyanate and water, polyisocyanate and There are a resinification catalyst having an action of promoting the reaction with a polyol, an isocyanurate forming catalyst having an action of promoting the trimerization of polyisocyanate, and the like.

  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. Further, as the resinification catalyst, 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 etc. are mentioned. Furthermore, examples of the isocyanuration catalyst include 2,4,6-tris (dimethylaminomethyl) phenol, N, N ′, N ″ -tris (dimethylaminopropyl) -hexahydro-s-triazine, and the like. These may be used alone or in combination of two or more, and among them, a resinification catalyst and a trimerization catalyst are preferably used.

<Liquid B>
(Polyisocyanate)
On the other hand, liquid B, which is another one of the two liquids constituting the ground injection chemical liquid composition according to the present invention, is prepared by using polyisocyanate as an essential component, as in the prior art. In the invention, the content of polyisocyanate in such B liquid is generally 70 to 100% by mass, preferably 80 to 100% by mass, more preferably 90 to 100% by mass. It is desirable that When the polyisocyanate content is less than 70% by mass, there is a problem that the strength of the cured reaction product is lowered. Therefore, it is desirable that the ratio of the polyisocyanate in the liquid B is high, and there is no problem even if the liquid B is composed of only the polyisocyanate.

  In the present invention, the polyisocyanate that is an essential component of the liquid B is an organic isocyanate compound having two or more isocyanate groups (NCO groups) in the molecule, such as diphenylmethane diisocyanate (MDI), Aromatic polyisocyanates such as polymethylene polyphenylene polyisocyanate (crude MDI), tolylene diisocyanate, polytolylene polyisocyanate, xylylene diisocyanate, naphthalene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; fats such as isophorone diisocyanate In addition to cyclic polyisocyanates, urethane prepolymers having isocyanate groups at the molecular ends, isocyanurate-modified products of polyisocyanates, carbodiimide-modified products It can be mentioned. These polyisocyanate components may be used alone or in combination of two or more. Among them, generally, MDI and crude MDI are preferably used from the viewpoints of reactivity, economy, handling, and the like.

  In the present invention, it is desirable that the foaming agent is not substantially blended in the liquid A and liquid B as described above, and therefore is not actively present in the reaction system. Here, substantially no foaming agent is blended, when the foaming agent is other than water, by quantitative analysis, the content of the foaming agent is less than 1 ppm, and a trace amount of foaming agent less than 1 ppm. Is detected as a foreign substance, and it is determined that no foaming agent is added. The quantitative analysis is performed using gas chromatography, liquid chromatography, or the like. In addition, when the blowing agent is water, water is intentionally added to the chemical composition separately from the water contained in the blended polyol, polyisocyanate, catalyst, and other additives. It means not to. Specifically, in the liquid A or the liquid B, if the amount of water present is less than 0.1% by mass, it is regarded as a foreign substance and it is determined that no foaming agent is blended.

  By the way, it is preferable that a flame retardant is contained in at least one of the liquid A and the liquid B as described above, which constitutes the chemical liquid composition according to the present invention. When this flame retardant is added to the liquid A, it is desirable that it is contained at a ratio of about 5 to 50 parts by mass, preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyol. Moreover, when adding to B liquid, it is desirable to make it contain in the ratio of about 5-40 mass parts with respect to 100 mass parts of polyisocyanate, Preferably it is 10-30 mass parts.

  Specific examples of such flame retardants include brominated flame retardants, chlorine-based flame retardants, phosphorus-based flame retardants, halogenated phosphates, and inorganic flame retardants. These may be used alone or in combination of two or more. Among these, phosphoric acid esters and halogenated phosphoric acid esters are preferably used in that they have a low environmental burden and function as a viscosity reducing agent for the foamable composition. Examples of the phosphate ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trixylenyl phosphate, and the like. Examples of the halogenated phosphate ester include tris (chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (dichloropropyl) phosphate, tetrakis (2-chloroethyl) dichloroisopentyl diphosphate, polyoxyalkylene bis. (Dichloroalkyl) phosphate and the like.

  In addition, it is possible to add various additives similar to those in the prior art to the liquid A and liquid B as described above constituting the chemical liquid composition according to the present invention, depending on the purpose of use. For example, a foam stabilizer, a viscosity reducing agent, etc. can be mentioned as an additive with respect to A liquid or B liquid. These additives are used in a proportion of 0.1 to 20 parts by mass, preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the polyol constituting the liquid A. Moreover, it will be used so that it may become a ratio of 0.1-15 mass parts with respect to 100 mass parts of polyisocyanate which comprises B liquid, Preferably it is 0.1-10 mass parts.

  Among these additives, the foam stabilizer is used to uniformly adjust the cell structure of the foam formed by the reaction between the liquid A and the liquid B. Examples of the foam stabilizer include silicone, nonionic surfactant, polyoxyalkylene-modified dimethylpolysiloxane, polysiloxaneoxyalkylene copolymer, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, lauryl fatty acid ethylene oxide. Additives and the like can be mentioned, and among these, silicone and nonionic surfactants are preferably used. These may be used alone or in combination of two or more. Of the foam stabilizers, silicone foam stabilizers are more preferred, and among them, polyoxyalkylene-modified dimethylpolysiloxane, polysiloxaneoxyalkylene copolymer, and the like are preferably used.

  In addition, the viscosity reducing agent is used as a solvent and is dissolved in the liquid A or the liquid B and has a function of reducing the viscosity of these liquids. Therefore, as long as it has such a function, it is not particularly limited. For example, alcohols such as methanol and ethanol, ethers such as ethyl cellsolve and butylcellsolve, and cyclic esters such as propylene carbonate , Esters such as dicarboxylic acid methyl ester, ethylene glycol monomethyl ether acetate, petroleum hydrocarbons and the like. These may be used alone or in combination of two or more.

  By the way, it is desirable that the liquid A and the liquid B prepared according to the present invention are prepared so that the viscosity at a temperature of 25 ° C. is 50 to 500 mPa · s, preferably 60 to 400 mPa · s. When the viscosity is higher than 500 mPa · s, the liquid A and the liquid B become viscous liquids, which causes problems such as poor fluidity during mixing. Moreover, when a viscosity becomes lower than 50 mPa * s, there exists a problem that it is easy to be diluted with water.

  In addition, when using the chemical composition for ground injection according to the present invention composed of the A liquid and the B liquid as described above, these two liquids are mixed at the time of use, and the target ground, rock, etc. A solid foundation is formed by being introduced by pouring or pouring or the like and cured by reaction. The mixing ratio (A: B) between the A liquid and the B liquid is appropriately determined according to the hydroxyl group content in the A liquid and the NCO group content in the B liquid. Therefore, A: B = 1: 0.5 to 1: 3, preferably 1: 1 to 1: 2.5. Also, the method of using these A and B solutions is not particularly limited as long as the two liquids can be reliably mixed immediately before their use, and conventionally known injection methods and pouring methods are known. However, it will be adopted as appropriate.

  And when these A liquid and B liquid are mixed, in the chemical | medical solution composition according to this invention, the hardening reaction product with a foaming ratio of 2 times or less will be formed. This expansion ratio is usually set to be 1 to 2 times, preferably 1 to 1.5 times, and more preferably 1 to 1.3 times. The lower the expansion ratio, the better. On the other hand, when the expansion ratio is larger than 2, there is a possibility that effective strength cannot be obtained.

  Moreover, when A liquid and B liquid are mixed and thrown into water, it will contact with the water used as a foaming agent, and a foaming ratio will become high, and is 2-15 times normally, Preferably it is 3-10 times Is set to be As a result, the chemical composition injected into the ground with spring water has a partial or thorough expansion of the portion that does not contact with water is suppressed to 2 times or less while the portion that contacts with water expands to 2 or more times. A stepwise foaming form will be realized. The reaction product injected into the ground at this time has a higher foaming ratio of the outer wetted part, but the inner part that does not wet the liquid has a high strength curing reaction product with a lower foaming ratio. Therefore, the strength that can sufficiently support the water pressure of spring water can be obtained.

  Hereinafter, some examples and comparative examples of the present invention will be shown to clarify the present invention more specifically. However, the present invention is not limited by the description of such examples. It goes without saying that it is not a thing. In addition to the following examples, the present invention includes various changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention, in addition to the specific description described above. It should be understood that improvements can be made.

  In addition, together with the characteristics (viscosity) of the liquid A and liquid B obtained in the following examples and comparative examples, the expansion ratio of the reaction product when the liquid A and the liquid B are mixed and subjected to reaction curing and the curing thereof. The following methods are used for time, strength of reaction products, foam curability and foaming ratio when reacted / foamed in water, and water turbidity and light transmittance after foaming in water: Measurement or evaluation. In addition, “%” and “part” shown below are based on mass.

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

(2) Foaming ratio Each of liquid A and liquid B adjusted to a temperature of 25 ° C. was measured so that the total amount would be 100 ml at a predetermined mixing ratio shown in Table 1 or Table 2 below. After storing the liquid in a 2 L disc, the mixture was sufficiently mixed and stirred to be cured. And about the reaction product after completion | finish of hardening reaction, the foaming height was measured and the expansion ratio was calculated | required.

(3) Curing time After mixing liquid A and liquid B adjusted to a temperature of 25 ° C. at the mixing ratio shown in Table 1 or Table 2, gas is generated from the reaction product, and the foaming height is The time at which no change occurred, or the time at which the reaction product was stabbed into the inside and was not pierced to the inside was measured, and the later of these was taken as the end point of curing time. Moreover, when hardening did not occur for 1 hour or more, it evaluated that it did not harden | cure.

(4) Strength After mixing and stirring the liquid A and liquid B at the mixing ratio shown in Table 1 or 2, the upper part was poured into a bottomed cylindrical mold having an inner diameter of 50 mm and a height of 120 mm, and 30 ° C. After curing for 24 hours, a specimen having a diameter of 50 mm and a height of 100 mm was cut out from the reaction product in the mold, and the compression strength was measured according to JIS-K-7220.

(5) Reaction Curability in Water Liquid A and liquid B adjusted to a temperature of 25 ° C. were weighed and mixed at a mixing ratio shown in Table 1 or Table 2 so that the total amount was 100 ml. Immediately after the mixing, the mixture of liquid A and liquid B was put into 1 L of 20 ° C. water contained in a 2 L disc cup and stirred 30 times in water using a spatula. The reaction product obtained was allowed to stand for a while and evaluated. The reaction product obtained was marked with ◯, the partially cured product was marked with Δ, and the product diluted with water and the reaction product was not obtained was marked with ×.

(6) Foaming ratio in water The foaming ratio was determined from the height of the reaction product obtained in the test of (5) above.

(7) Water turbidity Liquid A and liquid B adjusted to a temperature of 25 ° C. were weighed and mixed at a mixing ratio shown in Table 1 or Table 2 so that the total amount was 100 ml. Then, immediately after the mixing, the mixture was poured into 1 L of 20 ° C. water contained in a 2 L disc, stirred with water using a spatula 30 times, and allowed to stand until the reaction was completed. After the reaction had settled, the turbidity of the water was visually confirmed, and evaluation was made with ◎ indicating no turbidity, ○ indicating almost no turbidity, and × indicating apparently turbidity.

(8) Light transmittance The water in the disc used in the water turbidity test of (7) above is collected, and a spectrophotometer (U-2800 type spectrophotometer manufactured by Hitachi High-Technologies Corporation) is used for this. The light transmittance at a wavelength of 500 nm was measured.

Example 1
-Preparation of solution A-
As a polyol, polyether polyol manufactured by Sanyo Chemical Industries, Ltd .: PP-400 [initiator: propylene glycol, alkylene oxide: propylene oxide (PO) 100% by mass, molecular weight: 400, functional group number: 2, hydroxyl value: 280 mgKOH / g ], 100 parts thereof, 1.7 parts of PACCAT 15G (potassium catalyst: potassium octylate) manufactured by Nippon Chemical Industry Co., Ltd. as a metal catalyst, and TMCPP [Tris (manufactured by Daihachi Chemical Industry Co., Ltd.) as a flame retardant 30 parts of [chloropropyl) phosphate] were added and mixed uniformly to obtain Liquid A. And the viscosity of this obtained A liquid was measured, and the result was shown in following Table 1.

-Preparation of solution B-
As polyisocyanate, Wannate PM-200 (Polymeric MDI) manufactured by Wanhua Chemical Japan Co., Ltd. was used, and 100 parts thereof were prepared as B liquid. And the viscosity of this prepared B liquid was measured, and the result was shown in following Table 1.

-Reaction between liquid A and liquid B-
The liquid A and liquid B obtained above were combined at a volume ratio of 1: 1, and were uniformly mixed and reacted at room temperature. After that, various evaluations were made according to the evaluation methods described above. Tests were conducted and the results are shown in Table 1 below.

(Example 2)
In Example 1, the amount of the metal catalyst used was 1 part, and as a tertiary amine catalyst, Kao Riser No. Each evaluation test was performed in the same manner as in Example 1 except that 1 part of 31 (resinification catalyst: 33% triethylenediamine in dipropylene glycol solution) was further added. The obtained results are shown in Table 1 below.

Example 3
In Example 2, the polyol was a polyether polyol manufactured by Sanyo Chemical Industries, Ltd .: PP-3000 (initiator: propylene glycol, PO: 100% by mass, molecular weight: 3000, functional group number: 2, hydroxyl value: 35 mgKOH / g) In addition, an evaluation test was performed according to the same method as in Example 2 except that the amounts of the metal catalyst and tertiary amine catalyst used were 1.5 parts respectively. The obtained results are shown in Table 1 below.

(Example 4)
In Example 2, the polyol was changed to polyether polyol: GP-1000 (initiator: glycerin, PO: 100% by mass, molecular weight: 1000, functional group number: 3, hydroxyl value: 160 mgKOH / g) manufactured by Sanyo Chemical Industries, Ltd. An evaluation test was performed according to the same method as in Example 2 except that the conditions were changed. The obtained results are shown in Table 1 below.

(Example 5)
In Example 2, the polyol is replaced with polyether polyol manufactured by Adeka Corporation: BPX-2000 (initiator: bisphenol A, PO: 100% by mass, molecular weight: 2000, number of functional groups: 2, hydroxyl value: 57 mgKOH / g). In addition, an evaluation test was performed according to the same method as in Example 2 except that the usage amounts of the metal catalyst and the tertiary amine catalyst were 1.2 parts respectively. The obtained results are shown in Table 1 below.

(Example 6)
In Example 2, the polyol was changed to polyether polyol manufactured by Adeka Corporation: EDP-1100 (initiator: ethylenediamine, PO: 100% by mass, molecular weight: 1,100, functional group number: 4, hydroxyl value: 250 mgKOH / g). Except for this, an evaluation test was performed in the same manner as in Example 2. The obtained results are shown in Table 1 below.

(Comparative Example 1)
In Example 2, the polyol was changed to polyether polyol: GP-400 (initiator: glycerin, PO: 100% by mass, molecular weight: 400, functional group number: 3, hydroxyl value: 400 mgKOH / g) manufactured by Sanyo Chemical Industries, Ltd. In addition, an evaluation test was performed according to the same method as in Example 2 except that the amounts of the metal catalyst and tertiary amine catalyst used were 1.5 parts, respectively. The obtained results are shown in Table 2 below.

(Comparative Example 2)
In Example 2, as a polyol, 50 parts of the above-mentioned PP-400, polyether polyol manufactured by Adeka Corporation: EDP-450 (initiator: ethylenediamine, PO: 100% by mass, molecular weight: 450, functional group number: 4, (Hydroxyl value: 500 mg KOH / g) and 50 parts of the same as in Example 2 except that the amount of the metal catalyst used is 1.0 part and the amount of the tertiary amine catalyst is 0.7 parts. Each evaluation test was performed according to the method. The obtained results are shown in Table 2 below.

(Comparative Example 3)
In Example 2, the polyol was a polyether polyol manufactured by Sanyo Chemical Industries, Ltd .: GL-3000 (initiator: glycerin, PO: ethylene oxide (EO) = 80: 20, molecular weight: 3000, functional group number: 3, hydroxyl value. : 56 mgKOH / g), and an evaluation test was carried out in the same manner as in Example 2 except that the amount of the metal catalyst and tertiary amine catalyst used was 1.2 parts. The obtained results are shown in Table 2 below.

(Comparative Example 4)
In Example 2, as the polyol, 50 parts of the above-mentioned PP-400 and BM-54 manufactured by Sanyo Chemical Industries, Ltd. (initiator: ethylenediamine, PO: EO = 60: 40, molecular weight: 500, number of functional groups: 4, (Hydroxyl value: 450 mg KOH / g) In addition to using 50 parts, and using the metal catalyst and the tertiary amine catalyst in amounts of 0.25 parts, respectively, the evaluation test was performed in the same manner as in Example 2. went. The obtained results are shown in Table 2 below.

(Comparative Example 5)
In Example 2, the polyol was a polyether polyol manufactured by Sanyo Chemical Industries, Ltd .: BEO-10AE (initiator: bisphenol A, EO: 100% by mass, molecular weight: 670, number of functional groups: 2, hydroxyl value: 171 mgKOH / g) In addition, an evaluation test was performed in the same manner as in Example 2 except that the amount of the metal catalyst used was 0.5 part and the amount of the tertiary amine catalyst used was 0.3 part. The obtained results are shown in Table 2 below.

(Comparative Example 6)
In Example 2, the polyol was replaced with polyester polyol: RDK-133 (hydroxyl value: 315 mgKOH / g) manufactured by Kawasaki Kasei Kogyo Co., Ltd., and the usage amounts of the metal catalyst and the tertiary amine catalyst were each 0.5 parts. Except for this, an evaluation test was performed in the same manner as in Example 2. The obtained results are shown in Table 2 below.

(Comparative Example 7)
In Example 1, an evaluation test was performed according to the same method as in Example 1 except that no metal catalyst was added. The obtained results are shown in Table 2 below.

(Comparative Example 8)
In Example 2, an evaluation test was performed according to the same method as in Example 2 except that the metal catalyst was not added. The obtained results are shown in Table 2 below.

  As is clear from the results shown in Tables 1 and 2, in the chemical liquid composition comprising the combination of the liquid A and the liquid B according to Examples 1 to 6 according to the present invention, both of the foaming agents are substantially used. Since it was not contained, it was confirmed that the expansion ratio was low, and it was possible to express sufficient strength as a chemical solution composition for ground injection. Moreover, in the chemical composition composed of a combination of the liquid A and the liquid B, no turbidity of water after the reaction is completed while securing an appropriate expansion ratio in foaming in water. Since it is confirmed that the light transmittance at a wavelength of 500 nm is also good, there is little influence on the environment due to the reaction product being poured into water, and the cured reaction product is sufficient even when injected into the ground. It is recognized that a high strength can be obtained.

  On the other hand, in the combination of the liquid A and liquid B according to Comparative Examples 1 to 6, the hydroxyl value of the polyol of the liquid A used is not less than a specified value, and among the alkylene oxides added to the initiator In the foaming reaction of the liquid A and the liquid B in water, turbidity of the water after the reaction was observed. And from this, when using the combination of these A liquid and B liquid as a chemical composition for ground injection, it is predicted that the chemical liquid will flow into the water and there is a concern about adverse effects on the environment. there were. Moreover, in the chemical composition composed of the combination of the liquid A and the liquid B of Comparative Examples 7 and 8 that do not use a metal catalyst, none of them is cured, and the liquid A and the liquid B and the foaming reaction in water. However, it was thought that there was a problem in sufficient strength development as a chemical solution composition for ground injection because the curing was partially insufficient.

Claims (12)

In the chemical composition for ground injection comprising the A liquid mainly composed of polyol and the B liquid mainly composed of polyisocyanate,
95% by mass or more of the alkylene oxide added to the initiator is propylene oxide, and the polyol contains a polyether polyol having a hydroxyl value of 30 to 300 mgKOH / g at a ratio of 90% by mass or more. And the said A liquid contains the metal catalyst, The chemical | medical solution composition for ground injection | pouring characterized by the above-mentioned.   The said metal catalyst is contained in the ratio of 0.1-5 mass parts with respect to 100 mass parts of the said polyol, The chemical | medical solution composition for ground injection | pouring of Claim 1 characterized by the above-mentioned.   The chemical solution composition for ground injection according to claim 1 or 2, wherein the solution A further contains a tertiary amine catalyst.   The chemical solution composition for ground injection according to any one of claims 1 to 3, wherein a foaming agent is not substantially blended in the liquid A and the liquid B.   The chemical solution composition for ground injection according to any one of claims 1 to 4, wherein a curing reaction product having an expansion ratio of 2 times or less is provided.   The chemical composition for ground injection according to any one of claims 1 to 5, wherein the polyether polyol is obtained by adding an alkylene oxide to a polyhydric alcohol as an initiator.   7. The composition according to claim 1, wherein a content ratio of a polyether polyol obtained using an amine compound as an initiator in the polyol is 5% by mass or less. The chemical composition for ground injection according to claim 1.   The ground solution injection chemical composition according to any one of claims 1 to 7, wherein a flame retardant is contained in at least one of the liquid A and the liquid B.   The chemical composition for ground injection according to claim 8, wherein the flame retardant is contained in the liquid A at a ratio of 5 to 50 parts by mass with respect to 100 parts by mass of the polyol.   The said flame retardant is contained in the said B liquid in the ratio of 5-40 mass parts with respect to 100 mass parts of the said polyisocyanate, The chemical | medical solution composition for ground injection of Claim 8 characterized by the above-mentioned. .   11. The chemical composition for ground injection according to claim 1, wherein the viscosity of the liquid A and the liquid B at 25 ° C. is 50 to 500 mPa · s, respectively. .   The ground according to any one of claims 1 to 11, wherein the liquid A and the liquid B are used in a ratio of 1: 0.5 to 1: 3 on a volume basis. Chemical solution composition for injection.