JP2001011442A - Chemical for long tube injection method and long tube injection method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a chemical which can be used for modification of the ground and which can provide a desired cream time even when it is warm in the summer by combining a liquid A comprising a water glass, an amine-modified polyol and water as well as an imidazole-based catalyst as essential components and a liquid B comprising a polyisocyanate as an essential component. SOLUTION: A water glass is adjusted to have a solid content of 10-70 wt.% (hereinafter referred to as %) and incorporated in 50% or more of the liquid A. Amine-modified polyols include ethylenediamine, tolylenediamine, triethanolamine and the like and have a number average molecular weight of 150-1,000 and a hydroxy value of 200-450 mgKOH/g and are preferably incorporated in 10-50 pts.wt. (hereinafter referred to parts) based on 100 parts of the water glass. As an imidazole-based catalyst, 2-methylimidazole is preferred and incorporated in 1-5 parts based on 100 parts of the water glass. As a polyisocyanate, diphenylmethane-4,4'-diisocyanate can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a long tube injection method for use in a long tube injection method for injecting a chemical solution using a long tube, and a long tube injection method using the same. is there.

[0002]

2. Description of the Related Art In order to improve unstable ground (including ground, bedrock, etc.) into stable ground, a method of stably reinforcing a face of a tunnel which is easily collapsed requires a long pipe having a length of 12 m or more. A long tube injecting method of injecting a chemical solution by using the method is performed. In this long tube injection method, a urethane-based chemical solution comprising a liquid A prepared by mixing a polyol with a tertiary amine catalyst and a liquid B containing polyisocyanate as an essential component is used.

[0003]

However, in the long tube injection method using the above-mentioned chemical solution, when the liquid temperature becomes high (about 40 ° C.) in summer or the like, the reactivity between the liquid A and the liquid B becomes poor. As the cream time (foaming start time) becomes too fast, the chemical liquid foams inside the long tube, and the chemical liquid cannot penetrate and solidify into the surrounding ground. There is a drawback that you can not. This is because the tertiary amine catalyst has a high activity, adducts to isocyanate at the time of mixing, and immediately starts reacting with the polyol.

[0004] The present invention has been made in view of such circumstances, and it is possible to obtain a desired cream time and improve the ground even when the liquid temperature becomes high (about 40 ° C) in summer or the like. It is an object of the present invention to provide a chemical solution for a long tube injection method and a long tube injection method using the same.

[0005]

In order to achieve the above object, the present invention provides a liquid A containing water glass, an amine-modified polyol and water together with an imidazole catalyst, and a polyisocyanate as an essential component. A first aspect of the present invention is a chemical solution for a long tube injection method composed of the B solution.

A second aspect of the present invention is a method for injecting a long tube using the above-mentioned chemical solution.

That is, the present inventors have proposed a long pipe injection method which can obtain a desired cream time and improve the ground even when the liquid temperature becomes high (about 40 ° C.) in summer or the like. In order to obtain a chemical solution for use, we conducted intensive research. But,
If the cream time is slowed down, the foaming ratio will be reduced, and it will not be possible to satisfactorily improve the ground. Therefore, as a result of continuing research and development of a drug solution that can provide a sufficient foaming ratio even if the cream time is delayed, recalling that a good result can be obtained by using an imidazole-based catalyst, When an imidazole-based catalyst is used together with water glass, amine-modified polyol, and water as components, the cream time becomes slow even when the liquid temperature becomes high (about 40 ° C.) in the summer, etc. The present inventors have found that foaming can be prevented, foaming stability is excellent, and chemical solution can be penetrated and solidified into surrounding ground, and the present invention has been achieved. When the imidazole catalyst is used in this manner, the desired cream time and foaming ratio can be obtained because the reaction between water and isocyanate is slow, and the foaming and resinification reactions occur simultaneously, so that the desired cream time is obtained. This is because the foaming ratio is stable in time.

[0008] Of the above imidazole catalysts, when 2-methylimidazole is used, the cream time can be easily adjusted and the expansion ratio can be improved.

[0009]

Next, embodiments of the present invention will be described in detail.

The chemical solution for the long tube injection method according to the present invention is obtained by using a solution A containing an imidazole catalyst as an essential component together with water glass, an amine-modified polyol and water, and a solution B containing a polyisocyanate as an essential component. Can be.

The water glass, which is an essential component of the solution A, generally refers to a concentrated aqueous solution of an alkali silicate. The water glass is preferably adjusted to have a solid content concentration of 10 to 70% by weight, particularly preferably 40 to 6% by weight.
0% by weight.

[0012] The content of the water glass is 50% of the whole liquid A.
It is preferable to set the amount to not less than 60% by weight, particularly preferably in the range of 60 to 80% by weight. That is, when the content of the water glass is less than 50% by weight, the flame retardancy characteristic of the water glass system is impaired.

The amine-modified polyol used together with the water glass is not particularly limited as long as it is based on ethylenediamine, tolylenediamine, triethanolamine or the like.

The number-average molecular weight (Mn) of the amine-modified polyol is preferably in the range of 150 to 1,000, particularly preferably 400 to 900. That is, if it is less than 150, gelation tends to be fast and foaming tends to be difficult, whereas if it exceeds 1000, the reaction between polyol and isocyanate tends to be slow, and the balance with the foaming reaction tends to be poor. Because there is.

The above amine-modified polyol has a hydroxyl value (O
HV) is preferably in the range of 200 to 450 mgKOH / g, particularly preferably 250 to 400 mgKOH / g. That is, when it is less than 200 mgKOH / g,
The balance between the foaming (foaming) reaction and the resinification reaction deteriorates,
The expansion ratio tends to decrease, and conversely 450 mg KOH
This is because water / g tends to cause gelation of the water glass quickly and hardly foam.

The compounding amount of the amine-modified polyol is preferably set in the range of 10 to 50 parts, more preferably 15 to 25 parts, per 100 parts by weight of the water glass (hereinafter abbreviated as "part"). It is. That is, if it is less than 10 parts, foaming is difficult to be stabilized, and if it exceeds 50 parts, the viscosity tends to be too high or the cost tends to increase.

The water used together with the water glass and the polyol also serves as a foaming agent.

The amount of the water is preferably set in the range of 10 to 50 parts, more preferably 20 to 40 parts, per 100 parts of the water glass. That is, 1
If the amount is less than 0 part, the expansion ratio becomes small, and if it exceeds 50 parts, the obtained foam (urethane foam) becomes brittle or the amount of gas generated during the foaming reaction tends to be large, and it tends to collapse. Because there is.

The imidazole catalyst used together with the above water glass, amine-modified polyol and water includes:
There is no particular limitation, for example, 2-methylimidazole, 2
-Ethyl-4-methylimidazole, 2-isopropylimidazole, isobutyl-2-methylimidazole, etc., and these can be used alone or in combination of two or more. Among these, 2-methylimidazole is preferably used in terms of easy adjustment of the cream time and improvement in the expansion ratio.

The amount of the imidazole-based catalyst is preferably set in the range of 1 to 5 parts, more preferably 2.5 to 3 parts, based on 100 parts of the water glass.
That is, if the amount is less than 1 part, the expansion ratio tends to decrease, and if it exceeds 5 parts, the cream time (C
This is because T) tends to be too fast.

It is to be noted that an amine catalyst may be added to the liquid A. Examples of the amine catalyst include, for example,
Triethylenediamine, bis- (dimethylaminoethyl) ether, tetramethylhexamethylenediamine,
Tetramethylpropane-1,3-diamine, pentamethyldiethylenetriamine, bis (dimethylaminoethyl) ether, trimethylaminoethylpiperazine,
-Methylimidazole, 1-isobutyl-2-methylimidazole and the like. These can be used alone or 2
Used in combination of more than one species.

The amount of the amine catalyst is preferably set to 0.2 parts or less based on 100 parts of the water glass.

The liquid A may contain a foam stabilizer, a flame retardant or the like. Examples of the foam stabilizer include polyoxyalkylene / dimethylpolysiloxane copolymer, organopolysiloxane, oxyethylated higher alcohol, and the like.
Used in combination of more than one species. Examples of the flame retardant include trischloropropyl phosphate and tris-β-
Chloropropyl phosphate and the like can be mentioned, and these can be used alone or in combination of two or more.

The polyisocyanate which is an essential component of the solution B is not particularly limited. Examples thereof include diphenylmethane-4,4'-diisocyanate (MDI), polymeric MDI (C-MDI), tolylene diisocyanate (TDI), Hexamethylene diisocyanate (HD
I), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI) and the like. These may be used alone or in combination of two or more. Among them, MDI and C-MDI are preferably used.

The viscosity of the above polyisocyanate is 700
The temperature is preferably set to not more than cps / 25 ° C., particularly preferably in the range of 30 to 250 cps / 25 ° C. That is, when the temperature exceeds 700 cps / 25 ° C., the tendency to deteriorate the permeability is observed. The viscosity is a value measured using a single cylinder rotational viscometer.

The liquid B may contain a reactive diluent in addition to the polyisocyanate. Examples of the reactive diluent include alkylene carbonates such as ethylene carbonate and propylene carbonate, and dibasic acid esters.

The content of the above polyisocyanate is preferably set to 50% by weight or more of the whole liquid B, and particularly preferably 75% by weight or more.

The mixing ratio of the solution A and the solution B in the chemical solution for a long tube injection method of the present invention is expressed by weight ratio of the solution A: solution B =
It is preferable to set in the range of 1: 0.5 to 1: 2,
Particularly preferably, liquid A: liquid B = 1: 0.75 to 1: 1.5
It is.

The chemical solution for the long tube injection method of the present invention has a temperature of 40 ° C.
Is preferably 30 seconds or more, and particularly preferably 40 seconds or more. That is, if the cream time is less than 30 seconds, the chemical solution easily foams inside the long tube, and it becomes difficult to penetrate and solidify the chemical solution into the surrounding ground.

Further, the chemical solution for a long tube injection method of the present invention comprises:
The expansion ratio at 40 ° C. is preferably 8 times or more,
It is particularly preferably at least 10 times. That is, if the expansion ratio at 40 ° C. is less than 8 times, the ground cannot be sufficiently improved.

The long tube injection method of the present invention is carried out, for example, as follows. That is, first, a plurality of long holes 4 are formed on a roof 2 of a tunnel face tip 1 as shown in FIG. 1 using a rock drill such as a jumbo drill 3 as shown in FIG.
(Total length 20m, diameter 60-80mm). Next, as shown in FIG. 3, a long pipe 5 (5a is a chemical liquid discharge port formed at the tip end) is inserted into each long hole 4 up to the root, positioned, and positioned. The entrance of the hole 4 is sealed with a packer 6 such as cloth. At this time, Packer 6
A hose 7 for air bleeding and return which is opened in the long hole 4 is attached to the hole. Next, as shown in FIG.
A joint 8 with a check valve is attached to the rear end of each long pipe 5, a connection unit 9 with a forked pipe 10 is attached to this joint 8 with one touch, and hoses 11 and 12 are attached to the forked pipe 10, respectively. Next, the liquid A is supplied to one hose 11 from a pump (not shown) at a predetermined pressure (3 to 10 kg / cm ² ).
To supply it to the long tube 5, and to the other hose 12 the B solution from another pump (not shown) at a predetermined pressure (3 to 10k).
g / cm ² ) and supplied to the long tube 5. The two liquids thus injected are mixed in the hollow portion of the long tube 5,
The liquid is discharged from the chemical liquid discharge port 5a into the long hole 4. Then, after the discharged mixed liquid is filled in the long holes 4, the mixed liquid is further injected and permeated into gaps in the ground and cracks in the surrounding rock (see FIG. 5). If this penetration is done enough,
Since the pressures of both pumps suddenly increase, the injection of the chemical solution is stopped, and the connection unit 9 is removed. When the mixed liquid in the long holes 4 and the mixed liquid that has permeated the gaps between the ground and the cracks in the surrounding rock are completely solidified, the long pipes 5 are fixed in the long holes 4 and the bedrock around each of the long holes 4 is formed. (Ground mountain) is consolidated. 13
Is the obtained consolidation region. As a result, FIGS. 6 and 7
As shown in (1), the entire roof portion 2 is reinforced by the synergistic effect of the fixing of each long tube 5 and the consolidation region 13 around it.

The length of the long tube 5 is usually 12
m or more, and preferably in the range of 12 to 20 m.

Next, examples will be described together with comparative examples.

First, prior to Examples and Comparative Examples, the following materials were prepared.

[Water glass] Solid content: about 50% by weight

[Imidazole-based catalyst] 2-Methylimidazole (Curesol 2MZ, manufactured by Shikoku Chemicals)

[Tertiary amine catalyst] N, N, N ',
N ", N" -pentamethyldiethylenetriamine (Kaolyzer No. 3 manufactured by Kao Corporation)

[Amine-modified polyol] Tolylenediamine-based polyol (Actocol DT-250, manufactured by Takeda Pharmaceutical Co., Ltd.) [OHV: 255 mgKOH / g, molecular weight: 880]

[Polyisocyanate] C-MDI (Cosmonate MC-11, manufactured by Mitsui Chemicals, Inc.) [Viscosity: 56 cp
s / 25 ° C]

[0040]

Examples 1 to 5 and Comparative Examples 1 to 6 First, components A shown in Tables 1 and 2 described below were blended in proportions shown in the same table to prepare a solution A. Using the solution A and the solution B composed of the C-MDI (Cosmonate MC-11, manufactured by Mitsui Chemicals, Inc.), each characteristic was evaluated according to the following criteria. The results are shown in Tables 1 and 2 below.

[Cream Time (CT)] The above solution A and B
The liquid was mixed and the time until foaming started was measured.

[Expansion Ratio] A cup expansion test was performed to determine an expansion ratio. That is, 50 g of each of the liquids A and B was weighed, placed in a 1-liter disc, and stirred at a predetermined liquid temperature (20 ° C., 30 ° C., 40 ° C.) at 1000 rpm × with a stirrer (three-one motor). 1
The mixture was reacted by stirring for 0 second. Then, the foaming height (cm) after the completion of the reaction was measured to determine the foaming ratio.

[Injection Characteristics of Long Tube] (Shape) As shown in FIG.
1 is provided with a long test tube 82 having a length of 12.5 m and a sand tank 83 made of No. 4 silica sand (1 mx
1 m, length 15 m). Then, using a gear pump 84, the liquid A and liquid B were injected into the long test tube 82 at a liquid temperature of 30 to 40 ° C and a flow rate of 5 to 10 kg / min (A + B = about 100 kg). Several hours after the injection, the test long pipe 82 was dug out to evaluate the shape of the improved soil. The evaluation results are shown as ○ when the shape is cylindrical, and as × when the shape is not cylindrical.

(Permeability) The size (diameter) of the improved soil was measured and evaluated as follows. ◎: 30 cm or more in diameter ○: 20 to less than 30 cm in diameter △: 10 to less than 20 cm in diameter ×: less than 10 cm in diameter

[0045]

[Table 1]

[0046]

[Table 2]

From the results shown in Tables 1 and 2, since the chemical solution of the product of Example uses 2-methylimidazole,
It can be seen that the cream time (CT) at 40 ° C. is 30 seconds or more and the expansion ratio is high (8 times or more). Therefore,
The temperature of the chemical solution of the example product is high (about 40 ° C.) in the summer etc.
In this case, it is possible to prevent the chemical solution from foaming inside the long tube, and it is possible to satisfactorily improve the ground because of excellent foaming stability.

On the other hand, since the chemical solution of the comparative example product did not use 2-methylimidazole, the cream time (CT) at 40 ° C. was less than 30 seconds and the foaming ratio was low. Therefore, when the liquid temperature of the comparative example product becomes high temperature (about 40 ° C.) in summer or the like, the chemical liquid foams inside the long tube, so that the liquid chemical permeates and solidifies into the surrounding ground. Can not improve the ground.

[0049]

As described above, the chemical solution for the long tube injection method of the present invention comprises a solution A containing an imidazole catalyst together with water glass, an amine-modified polyol and water, and a polyisocyanate as an essential component. It is composed of liquid B. As described above, by using the imidazole-based catalyst in combination, even when the liquid temperature becomes high (about 40 ° C.) in summer or the like, the cream time is delayed, and it is possible to prevent the chemical solution from foaming inside the long tube. At the same time, the foaming stability is excellent, and the penetration of the chemical solution into the surrounding ground can be achieved.

When 2-methylimidazole is used among the above-mentioned imidazole catalysts, the cream time can be easily adjusted and the expansion ratio can be improved.

[Brief description of the drawings]

FIG. 1 is a front view of a roof part at the tip of a tornell face.

FIG. 2 is a schematic view showing a state in which a long hole is formed in the roof.

FIG. 3 is a schematic view showing a state where a packer is attached to the base of the long hole.

FIG. 4 is a schematic view showing a state where a joint or the like is attached to the long pipe.

FIG. 5 is a schematic diagram showing a state in which a chemical solution is being discharged from the long tube.

FIG. 6 is an explanatory diagram of a solidification region of a chemical solution.

FIG. 7 is an explanatory diagram of a solidification region of a chemical solution.

FIG. 8 is an explanatory diagram of a method for evaluating long tube injection characteristics.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) E21D 9/04 E21D 9/04 F // C09K 103: 00 (72) Inventor Noboru Mizuno Komaki, Aichi Prefecture No. 3600, Gezu, Kita-gaiyama Tokai Rubber Industries Co., Ltd. F-term (reference) 2D040 AB01 AB06 AB14 BB09 CA02 CA10 CB03 CD06 DA01 DC02 2D054 AB07 AC15 FA02 4H026 CA03 CA06 CB08 CC06

Claims (6)

[Claims] 1. A chemical solution for a long tube injection method, comprising a liquid A containing water glass, an amine-modified polyol and water together with an imidazole catalyst as an essential component, and a liquid B containing polyisocyanate as an essential component. 2. The method according to claim 1, wherein the imidazole-based catalyst is 2-methylimidazole. 3. The chemical solution for a long pipe injection method according to claim 1, wherein the amount of the imidazole-based catalyst is set in a range of 1 to 5 parts by weight based on 100 parts by weight of the water glass. . 4. The chemical solution for long tube injection method according to claim 1, wherein a cream time (foaming start time) at 40 ° C. is 30 seconds or more. 5. The chemical solution for a long tube injection method according to claim 1, wherein the expansion ratio at 40 ° C. is 8 times or more. 6. A method for injecting a long tube, comprising using the drug solution according to claim 1.