JP6823040B2 - Composition for lock bolt fixing material, lock bolt fixing material and lock bolt method - Google Patents

Description

The present invention relates to a composition for a lock bolt fixing material, a lock bolt fixing material, and a lock bolt method.

In mountain tunnel excavation work, various auxiliary methods such as AGF method, injection type fore polling method, and face bolt method to further improve safety during excavation and rock bolt method to suppress deformation of the tunnel after excavation. Two types of construction methods are adopted.

The AGF method and the injection type fore polling method are construction methods that stabilize the soil quality in the upper part of the front in order to prevent the edge from collapsing during excavation, and ensure safety from excavation to lining concrete placement. .. In addition, the face bolt construction method is a construction method that stabilizes the mirror surface, which is the excavation cross section, and the soil quality in front of it, and ensures safety from the completion of excavation in a certain section to the start of the next excavation. These auxiliary construction methods are aimed at improving the safety of excavation work.

The rock bolt method is a method that stabilizes the surrounding ground after excavating a tunnel. By fixing the bolts to the ground with a fixing material, the lining concrete to be placed after that and the ground movement due to earthquakes, etc. It is done for the purpose of protecting the tunnel structure. Therefore, the fixing material for fixing the lock bolt to the surrounding ground is required to have high strength and long-term durability to ensure safety during use of the tunnel structure, and various assists during the excavation are required. It is very different from the ground consolidation material used in the construction method.

Conventionally, an inorganic material such as mortar having high strength has been used as such a lock bolt fixing material. However, these inorganic materials have a problem that the work efficiency is not sufficient because it takes a long time to develop the strength, and the material flows out into the water when water leakage or spring water occurs. It was.

Therefore, in order to solve these problems, an organic-inorganic composite material composed of an aqueous alkali silicate solution and an isocyanate compound is used as a fixing material (see Patent Documents 1 and 2).

JP-A-2002-285155 Japanese Unexamined Patent Publication No. 2011-37946

However, the fixing material of Patent Document 1 has problems of long-term durability and water pollution. Further, in recent years, there has been a demand for a foam type fixing material that can easily fill the gap between the rock bolt and the surrounding ground from the viewpoint of cost reduction and improvement of the fixing property between the rock bolt and the surrounding ground. A fixing material having sufficient physical properties has been required even at a foaming ratio higher than that of the fixing material of Patent Document 2. The present invention has been made in view of the above, and is a composition for a rock bolt fixing material which is a foaming type, has less water pollution, has sufficient strength, long-term durability, and has a sufficient strength development rate. An object of the present invention is to provide a lock bolt fixing material in which the composition is cured.

As a result of diligent studies, the present inventors have obtained a chemical solution composition composed of a component (A) containing a predetermined polyol and a predetermined amine compound and a component (B) containing an isocyanate compound. We have found that the above problems can be solved, and have completed the present invention through further studies.

That is, the present invention
[1] A composition for a rock bolt fixing material to be cast on the surrounding ground after excavating a tunnel, wherein the fixing material composition contains a polyol, an amine compound, and water (c) (A). And the component (B) containing an isocyanate compound, the polyol contains a polyether polyol (a1), and the amine compound is diethyltoluenediamine, diethanolamine, 1,2-propanediamine, and the like. Those containing at least one amine compound (b1) selected from the group consisting of 3-aminomethyl-3,5,5-trimethylcyclohexylamine, hexamethylenediamine, and terminal aminated propylene glycol (weight average molecular weight less than 2000). The composition for rock bolt fixing material, wherein the content of the water (c) is 0.3 parts by mass to 2.5 parts by mass with respect to 100 parts by mass of the component (A).
[ 2 ] The composition for a rock bolt fixing material according to the above [1], wherein the viscosities of the components (A) and (B) are both 650 mPa · Sec or less at 25 ° C.
[ 3 ] A lock bolt fixing material obtained by curing the composition for a lock bolt fixing material according to the above [1] or [2] .
[ 4 ] A step of drilling a plurality of holes in the bedrock or the ground at predetermined intervals, a step of inserting a bolt and an injection rod having no voids in the holes, and the above [1] or [2 ] from the injection rod. ] , Which comprises a step of injecting the composition for a rock bolt fixing material according to any one of the above items into a bedrock or the ground and solidifying the rock bolt method.
Regarding.

According to the present invention, a composition for a lock bolt fixing material having a foaming type, less water pollution, sufficient strength, long-term durability, and a sufficient rate of onset of strength, and a lock bolt obtained by curing the composition. A fixing material can be provided.

Further, it is preferable to add castor oil-based polyester polyol (a2) to the component (A) because the foaming ratio can be more preferably controlled.

Each element constituting the present invention will be described below.

<Ingredient (A)>
In the present invention, the component (A) comprises a polyol, an amine compound and water (c). Here, the polyol contains a polyether polyol (a1), and can also contain a castor oil-based polyester polyol (a2). On the other hand, the amine compound contains an amine compound (b1) having a primary or secondary amino group, and may further contain a tertiary amine compound (b2).

(Polyether polyol (a1))
The polyether polyol (a1) used in the present invention is not particularly limited, and for example, monools such as methanol, ethanol, propanol, butanol, octanol, and lauryl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol. Diols such as dipropylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, polyols such as glycerin, trimethylolpropane, pentaerythritol; and other monoethanolamine and diethanolamine. , Triethanolamine, diglycerin, sorbitol, sucrose and other active hydrogen-containing compounds, or a mixture thereof, using one or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide and styrene oxide, and known. Examples thereof include monool or polyol obtained by addition polymerization by the above method.

Further, a hydroxyl group-terminated urethane prepolymer obtained by reacting the monool or polyol with an isocyanate compound described later can also be used.

Of these, a polyether polyol obtained by addition-polymerizing propylene oxide to glycerin, a polyether polyol obtained by addition-polymerizing propylene oxide to propylene glycol, and a polyether polyol obtained by addition-polymerizing propylene oxide to sorbitol are preferable.

The weight average molecular weight (Mw) of these polyether polyols (a1) is preferably 800 or less, more preferably 650 or less, from the viewpoint of maintaining workability and compressive strength of the cured product. It is more preferably 500 or less.

In the present invention, the weight average molecular weight is a value measured by the GPC method. As the GPC method, for example, HLC-8020 manufactured by Tosoh Corporation is used as the GPC main body, the column temperature is 40 ° C., the pump flow rate is 0.6 to 1.0 ml / min, and the detector is RI (built into the GPC main body). [Column: TSKgel G6000H HR + G4000H HR + G3000H HR + G2000H HR (used by connecting 4); Mobile phase: THF; Injection amount: 80 μl; Sample concentration: 0 .2% (w / v)]. In this method, for example, the molecular weight can be determined as the PPG-equivalent molecular weight by using a calibration curve of a standard PPG whose molecular weight is known in advance (calibration at a molecular weight of 250 or more).

In these polyether polyols (a1), the number of functional groups (number of hydroxyl groups) is preferably 3 or less from the viewpoint of workability.

The polyether polyol (a1) can be used alone or in combination of two or more.

The content of the polyether polyol (a1) is preferably 50 to 95% by mass, more preferably 55 to 90% by mass, based on the total amount of the component (A). If it is less than 50% by mass and more than 95% by mass, the compressive strength of the rock bolt fixing material tends to decrease.

(Castor oil-based polyester polyol (a2))
The castor oil-based polyester polyol (a2) used in the present invention is produced using castor oil, castor oil fatty acid, hydrogenated castor oil added to castor oil, or hydrogenated castor oil fatty acid added to castor oil fatty acid. It is a polyol. Examples of such castor oil-based polyester polyol (a2) include castor oil, an ester exchange product of castor oil and other natural fats and oils, a reaction product of castor oil and polyhydric alcohol, and castor oil fatty acid and polyhydric alcohol. Esterization reaction product, hydrogenated castor oil, ester exchange of hydrogenated castor oil and other natural fats and oils, reaction product of hydrogenated castor oil and polyhydric alcohol, ester of hydrogenated castor oil fatty acid and polyhydric alcohol Examples thereof include chemical reaction products and polyols obtained by addition-polymerizing alkylene oxide to these. Of these, castor oil is the most preferable.

In the present invention, by using these castor oil-based polyester polyols (a2), the foaming ratio of the rock bolt fixing material is not excessively increased, and therefore, the environment when the cured product flows out due to water leakage or spring water. Sufficient strength, long-term durability, and sufficient strength development rate can be obtained with little adverse effect on.

In these castor oil-based polyester polyols (a2), the Mw thereof is preferably 800 or less, more preferably 650 or less, and more preferably 500 or less, from the viewpoint of maintaining workability and compressive strength of the cured product. It is even more preferable to have.

In these castor oil-based polyester polyols (a2), the number of functional groups (number of hydroxyl groups) is preferably 3 or less from the viewpoint of workability.

The castor oil-based polyester polyol (a2) can be used alone or in combination of two or more.

The content of the castor oil-based polyester polyol (a2) is preferably 0 to 45% by mass, more preferably 10 to 30% by mass, based on the total amount of the component (A). If it exceeds 45% by mass, the compressive strength of the cured product tends to decrease.

(Content ratio (a1) / (a2))
The content ratio (mass ratio) of the polyether polyol (a1) and the castor oil-based polyester polyol (a2) is (a1) / (a2) of 1.3 or more, more preferably 1.5 or more, still more preferable. Is 3.5 or higher. If it is less than 1.3, the compressive strength of the cured product tends to decrease. The content ratio is most preferably about 4.0. In this case, "about" means to allow a fluctuation of about ± 0.1.

(Amine compound (b1))
The amine compound (b1) having a primary or secondary amino group used in the present invention is not particularly limited, but for example, monomethylamine, monoethylamine, monobutylamine, dimethylamine, diethylamine, din-propylamine, diisopropyl. Alkyl monoamines such as amines, dibutylamines, diamylamines, dihexylamines, methylethylamines, methylpropylamines, methylisopropylamines, ethylpropylamines, ethylisopropylamines, N-methyldodecylamines, bis (2-ethylhexyl) amines; monoethanolamines. Alcanol monoamines such as diethanolamine and diisopropanolamine; alicyclic monoamines such as cyclopentylamine, cyclohexylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, or dicyclohexylamine; N-methylbenzylamine, dibenzylamine, benzyl Aromatic monoamines such as amines, p-methylbenzylamine; heterocyclic monoamines such as morpholin, pyrrolidine, piperidine or 1H pyrazole; hydrazine; ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, tetramethylenediamine, Alibo diamines such as hexamethylenediamine, heptamethylenediamine, octamethylenediamine, neopentanediamine; 4,4'-diaminocyclohexylmethane, isophoronediamine, bisaminomethylcyclohexane, 2,5- or 2,6-diaminomethylbicyclo [2,2,1] Alicyclic diamines such as heptane, diaminocyclohexane, diethyltoluenediamine; diaminodiphenylmethane, diaminodiphenyl ether, xylylene diamine, phenylenediamine, 3,5-diethyl-2,4-diaminotoluene, 3, Aromatic diamines such as 5-diethyl-2,6-diaminotoluene; aliphatic triamines such as diethylenetriamine; 1,3,5-tris (aminomethyl) benzene, 1,3,5-tris (aminomethyl) cyclohexane and the like. Aromatic or alicyclic triamine; polyoxy obtained by converting the hydroxyl group of polyoxyalkylene glycols obtained by addition polymerization of propylene oxide and / or ethylene oxide to water, ethylene glycol, propylene glycol, etc. to an amino group. Alkylenediamine; propire to glycerin, trimethylpropane, etc. Examples thereof include polyoxyalkylene triamines obtained by converting the hydroxyl groups of polyoxyalkylene triols obtained by addition polymerization of phosphate and / or ethylene oxide into amino groups.

Of these, diethyltoluenediamine, diethanolamine, 1,2-propanediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, hexamethylenediamine, and terminal amination propylene glycol (weight average molecular weight less than 2000). Is preferable.

These amine compounds (b1) can be used alone or in admixture of two or more.

The content of the amine compound (b1) is preferably 2 to 12% by mass, more preferably 3 to 10% by mass, based on the total amount of the component (A). If it is less than 2% by mass, it tends to be difficult to suppress cloudiness, and if it exceeds 12% by mass, the load applied to the mixer bolt or the like during construction tends to increase.

(Tertiary amine compound (b2))
In the present invention, known tertiary amine compounds (b2) can be used without particular limitation, and for example, N, N-dimethyloctylamine, N, N-dimethyllaurylamine, N, N, N'. , N'-tetramethylhexamethylenediamine, N, N, N', N'-tetramethylpropylenediamine, N, N, N', N'-tetramethylethylenediamine, N, N, N', N', N ''-Pentamethyldiethylenetriamine, trimethylaminoethylpiperazine, bis- (dimethylaminoethyl) ether, hexahydro-S-triazine, triethanolamine, triethylenediamine, 2-methyltriethylenediamine, N, N-dimethylaminoethylmorpholine, dimethyl Examples thereof include aminopropyl imidazole, hexamethyltriethylenetetramine, hexamethyltripropylenetetramine, N, N, N-tris (3-dimethylaminopropyl) amine and the like.

These tertiary amine compounds (b2) can be used alone or in admixture of two or more.

The content of the tertiary amine catalyst (b2) is preferably 0.3 to 10% by mass, more preferably 0.5 to 7% by mass, based on the total amount of the component (A). If it is less than 0.3% by mass, workability tends to deteriorate, and if it exceeds 10% by mass, the load applied to the mixer bolt or the like during construction tends to increase.

The content of water (c) used in the present invention is 0.3 parts by mass to 2.5 parts by mass with respect to 100 parts by mass of the component (A). It is preferably 0.5 parts by mass to 1.5 parts by mass, and more preferably 0.7 parts by mass to 1.0 parts by mass. Within these ranges, the adverse effect on the environment when the cured product flows out due to water leakage or spring water is small, and sufficient strength, long-term durability, and sufficient strength development rate can be obtained.

(Other ingredients)
In addition to the above-mentioned components, the component (A) according to the present invention includes, if necessary, a silicon-based defoaming agent, a diluent, a flame retardant, a pigment, an inorganic filler, a cross-linking agent, a coupling agent, and the like. Known additives can be added as long as the object of the present invention is not impaired.

The silicon-based foam stabilizer is not particularly limited, and examples thereof include a polyoxyalkylene dimethylpolysiloxane copolymer usually used for a rigid urethane foam resin.

The diluent is not particularly limited, and for example, phthalates such as dibutyl phthalate, dioctyl phthalate, and diisononyl phthalate, dibutyl adipate, dioctyl adipate, diisononyl adipate, and bis (2- (2-butoxyethoxy) ethyl) adipate. Examples thereof include trimellitic acid esters such as adipate ester and tri (2-ethylhexyl) trimellitate. Of these, bis (2- (2-butoxyethoxy) ethyl) adipate and tri (2-ethylhexyl) trimeritate are preferable because they have little impact on the environment and are excellent in safety.

The flame retardant is not particularly limited, and for example, either an additive type or a reactive type can be used. Specific examples of the addition type include phosphorus-containing halogen-containing systems such as tributyl phosphate, tricresyl phosphate, and trismonochloroisopropyl phosphate; and halogen-containing systems such as chlorinated paraffin, pentabromoethylbenzene, and decabromodiphenyl ether. can give. Specific examples of the reactive type include halogen-containing phosphorus-containing compounds having hydroxyl groups or amino groups such as dibromoneopentyl glycol, tetrabromobisphenol A, diethyl N, N-dihydroxyethylaminomethylphosphotate, and various phosphorus-containing polyols. And so on.

In the present invention, it is preferable not to use a diluent from the viewpoint of suppressing adverse effects on the environment due to bleed-out.

(viscosity)
In the present invention, the viscosity of the component (A) is preferably 650 mPa · sec or less, more preferably 600 mPa · sec or less, still more preferably 450 mPa · sec or less at 25 ° C. from the viewpoint of workability. is there.

<Ingredient (B)>
In the present invention, the component (B) contains an isocyanate compound.

(Isocyanate compound)
The isocyanate compound is not particularly limited, and is, for example, diphenylmethane diisocyanate and its isomer, polymethylene polyphenyl polyisocyanate (polymeric MDI), tolylene diisocyanate, crude tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, water. Alone or a mixture of polyisocyanates such as supplemented diphenylmethane diisocyanate and trimethylenexylylene diisocyanate; carbodiimide-modified products of these polyisocyanates and dimers or trimerics by adding a catalyst: These polyisocyanates are used as the polyether. Examples thereof include an isocyanate group-terminated urethane prepolymer alone or a mixture obtained by reacting with a polyol (a1) or an oil-based polyester polyol (a2).

Among these, polymethylene polyphenyl polyisocyanate (polymeric MDI) and this isocyanate group-terminated urethane prepolymer are preferable from the viewpoint of cloudiness.

These isocyanate compounds can be used alone or in admixture of two or more.

(Other ingredients)
As other components, the conventionally known additives described in the section of component (A) can be added to the component (B) according to the present invention as necessary without impairing the object of the present invention. ..

(viscosity)
In the present invention, the viscosity of the component (B) is preferably 650 mPa · sec or less, more preferably 600 mPa · sec or less, still more preferably 450 mPa · sec or less at 25 ° C. from the viewpoint of workability. is there.

Next, the lock bolt fixing material of the present invention will be described. The lock bolt fixing material of the present invention is obtained by curing the composition for the lock bolt fixing material.

(mixing ratio)
The mixing ratio of the component (A) and the component (B) according to the present invention is the reaction equivalent ratio of the OH group and NH ₂ group of the polyol in the component (A) and the NCO group in the component (B), that is, (OH + NH ₂ ) / NCO is preferably in the range of 1/5 to 5/1, more preferably 1/3 to 2/1. When the reaction equivalent ratio is larger than the above range, the cured product tends to be soft and its strength tends to be very small, and when it is smaller than the above range, the curing time becomes long and the lock bolt is fixed. The strength of the material is low and it tends to be brittle.

(Gel time)
The composition for a rock bolt fixing material of the present invention preferably has a gel time of 25 to 55 seconds when the component (A) and the component (B) adjusted to 20 ° C. are mixed. If the gel time is less than 25 seconds, workability tends to deteriorate, while if it exceeds 55 seconds, cloudiness tends to occur, which is not preferable. Here, the gel time is the time until gelation (that is, curing progresses and stringing) when the components (A) and (B) having a total amount of 30 g are mixed at 20 ° C. by hand mixing. Time to start).

(Expansion magnification)
The lock bolt fixing material of the present invention has a small adverse effect on the environment when the cured product flows out due to water leakage or spring water, and the cured product is free from the viewpoint of obtaining sufficient strength, long-term durability, and sufficient strength development rate. The foaming ratio is preferably low, for example, 30 times or less, more preferably 20 times or less, still more preferably 15 times or less. On the other hand, the lower limit of the foaming ratio is not particularly limited, but is usually 2 times or more. In the present invention, the foaming ratio is a value calculated by dividing the volume of the cured product after the completion of the curing reaction by the volumes of the components (A) and (B) as raw materials. The foaming ratio is measured by mixing the component (B) with the component (A) and foaming. Within these ranges, the foaming ratio when injected into the ground is 5 times or less, preferably 3 times or less, so that sufficient strength, long-term durability, and sufficient strength development rate can be obtained. ..

(Compression strength)
The compressive strength of the lock bolt fixing material of the present invention in free foaming is preferably 0.3 MPa or more, more preferably 0.4 MPa or more, from the viewpoint of obtaining sufficient strength and long-term durability. The compressive strength of the cured product is as follows: For the cured product obtained by mixing and curing the component (A) and the component (B), a test piece of 10 mm × 10 mm × 10 mm is cut out in accordance with JIS A 9511, and the instron is universal. It is measured with a testing machine.

(PH)
In the present invention, after the components (A) and (B) are mixed, the mixture is added to 10 times the amount of water, and after the reaction is completed, the supernatant is collected and the pH measured is 5 to 9. It is preferable to have.

<Rock bolt method>
The rock bolt fixing material composition and the rock bolt fixing material of the present invention are used as a fixing material when fixing a bolt to the ground, for example, in a rock bolt method for stabilizing the surrounding ground after tunnel excavation. .. By fixing the porto, it is possible to protect the tunnel structure from ground movement due to an earthquake or the like together with the lining concrete to be placed after that.

The method of injecting and solidifying the fixing material is not particularly limited, and a known method can be adopted. However, in the step of drilling a plurality of holes in the ground at predetermined intervals, a lock bolt is inserted into the holes. It is preferable to consist of a step and a step of injecting the composition for the lock bolt fixing material into the ground and consolidating it.

As an example of the process of injecting into the ground and solidifying, for example, a method using a comparative compounding pump capable of controlling the injection amount, pressure, compounding ratio, etc. of the components (A) and (B), etc. There is. In this method, the component (A) and the component (B) are placed in separate tanks and fixed in advance in a predetermined place such as a bedrock (for example, a plurality of holes drilled at intervals of about 0.5 to 3 m). Through an injection rod equipped with a static mixer, a check valve, etc., each component in the tank is injected into the injection rod at an injection pressure of 0.05 to 25 MPa, and the component (A) is mixed with a predetermined amount through the static mixer. (B) The components are uniformly mixed, injected into the ground, and solidified.

For example, when injecting into the top of a tunnel, prior to the injection, for example, a leg of about 1 m in the excavation direction and a leg of 42 mmφ bit, for example, at a predetermined interval according to the ground, although not specifically limited in the cross-sectional direction. A hole was drilled using an auger to provide an injection hole with a depth of 3 m and a drilling angle of 90 °, and a lock bolt having a length of 3 m and a static mixer and a check valve was inserted into the injection hole. In order to prevent backflow of the injected chemical solution, it is preferable to seal the mouth of the lock bolt with a waste cloth, a foamed hard urethane resin or the like, and inject the chemical solution by the above method. The injection operation ends when the injection pressure rises sharply, or when the injection amount is further increased by about 50% from the predetermined injection amount. Generally, it is preferable to inject 0.5 to 5.0 kg of the drug solution per injection hole.

The present invention will be described in detail based on examples, but the present invention is not limited thereto.

<Ingredients used>
(Polyether polyol (a1))
Polyester (a1-1): Polyether polyol having an average hydroxyl value of 480 mgKOH / g obtained by addition polymerization of propylene oxide to glycerin (trade name: DK polyol G480, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
Polyester (a1-2): Polyether polyol having an average hydroxyl value of 280 mgKOH / g obtained by addition polymerization of propylene oxide to propylene glycol (trade name: Hiflex D400, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
Polycarbonate (a1-3): Polyether polyol having an average hydroxyl value of 550 mgKOH / g obtained by addition polymerization of propylene oxide to sorbitol (trade name: Excelol 550SO, manufactured by Asahi Glass Co., Ltd.)
Polyester (a1-4): Polyether polyol having an average hydroxyl value of 56 mgKOH / g obtained by addition polymerization of propylene oxide to glycerin (trade name: Hiflex G3000C, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

(Castor oil-based polyester polyol (a2))
Polyol (a2-1): castor oil (trade name: castor oil D, manufactured by Ito Oil Co., Ltd.)
Polyester (a2-2): Castor oil-based polyester polyol having 1 functional group and an average hydroxyl value of 160 (trade name: URIC H-31, manufactured by Ito Oil Co., Ltd.)
Polyester (a2-3): Castor oil-based polyester polyol having 3 functional groups and an average hydroxyl value of 200 (trade name: URIC H-52, manufactured by Ito Oil Co., Ltd.)
Polyester (a2-4): Castor oil-based polyester polyol having 3 functional groups and an average hydroxyl value of 340 (trade name: URIC H-81, manufactured by Ito Oil Co., Ltd.)
Polyester (a2-5): Castor oil-based polyester polyol having 5 functional groups and an average hydroxyl value of 320 (trade name: URIC H-102, manufactured by Ito Oil Co., Ltd.)

(Amine compound having a primary or secondary amino group (b1))
Amine compound (b1-1): Diethyl toluenediamine (trade name: DETDA80, manufactured by Lonza Japan Co., Ltd.)
Amine compound (b1-2): Diethanolamine (manufactured by Nippon Shokubai Co., Ltd.)
Amine compound (b1-3): 1,2-propanediamine (manufactured by Wako Pure Chemical Industries, Ltd.)
Amine compound (b1-4): 3-aminomethyl-3,5,5-trimethylcyclohexylamine (manufactured by Wako Pure Chemical Industries, Ltd.)
Amine compound (b1-5): Hexamethylenediamine (manufactured by Nacalai Tesque, Inc.)
Amine compound (b1-6): Terminal aminated polypropylene glycol (trade name: Jeffamine D-2000, manufactured by Huntsman)

(Amine compound having a tertiary amino group (b2))
Amine compound (b2-1): Triethanolamine (manufactured by Nippon Shokubai Co., Ltd.)
Amine compound (b2-2): Triethylenediamine (trade name: TEDA-L33, manufactured by Tosoh Corporation)

(Water (c))
water

(Isocyanate compound)
Isocyanate compound 1: Polymeric MDI (trade name: Foamlite 200B, manufactured by BASF INOC Polyurethane Co., Ltd.)
Isocyanate compound 2: Polymeric MDI (trade name: Foamlite 500B, manufactured by BASF INOC Polyurethane Co., Ltd.)

<Preparation of agent A and agent B>
Agent A and agent B were prepared by appropriately mixing the raw materials according to the formulation shown in Table 1, with the solution composed of the component (A) as the agent A and the solution composed of the component (B) as the agent B.

(viscosity)
The viscosities (mPa · Sec) at 25 ° C. of Agents A and B were measured with a BL type viscometer (manufactured by Toki Sangyo Co., Ltd.) according to JIS K-7117-1.

<Evaluation of cured product>
(Gel time)
Agents A and B prepared according to the formulations shown in Table 1 were separately prepared at the mixing ratios shown in Table 1 so as to have a total of 30 g. After the temperatures of both the A and B agents were set to 20 ° C., the A and B agents were mixed by hand mixing, and the gel time (the time when curing progressed and stringing started) was measured.

(Foaming reactivity / foaming magnification)
Agents A and B prepared according to the formulations shown in Table 1 were separately prepared at the mixing ratio shown in Table 1 so as to have a total of 30 g. After the temperatures of both the A and B agents were set to 20 ° C., the A and B agents were mixed by hand mixing, and the foaming start time and foaming end time were measured. After completion of the curing reaction, the foaming ratio was calculated by dividing the volume of the cured product by the initial volumes of the raw materials A and B.

(Compression strength)
Agents A and B prepared according to the formulations shown in Table 1 were separately prepared at the mixing ratio shown in Table 1 so as to have a total of 30 g. After the temperatures of both the A and B agents were set to 20 ° C., the A and B agents were mixed by hand mixing to obtain a cured product. A 10 mm × 10 mm × 10 mm test piece was cut out from the cured product and measured with an Instron universal testing machine in accordance with JIS A 9511.

<Underwater cloudiness test>
Agents A and B prepared according to the formulations shown in Table 1 were separately prepared at the mixing ratio shown in Table 1 so as to have a total of 30 g. After both the A and B agents were brought to 20 ° C., the prepared A and B agents were mixed by hand mixing for 10 seconds, and then the mixture was immediately put into a container containing 300 g of water. The container was covered, and 30 seconds after the start of mixing the A and B agents, the entire container was vigorously shaken up and down and continued for 10 seconds. After the foaming is completed, water is collected from the container, and the turbidity of the water is visually measured and measured with a spectrophotometer (Hitachi spectrophotometer U-3900H (manufactured by Hitachi High-Technologies Corporation)). Light transmittance (%) at 500 nm. )). The transmittance is preferably 50% or more.

The results are shown in Table 1.

<Experimental example>
A lock bolt with a depth of 3 m and a drilling angle of 90 °, which was drilled in the top of the tunnel using a 42 mmφ bit leg auger, with a static mixer and a check valve installed in the injection hole. Was inserted, and the formulation of Example 1 was injected until the injection pressure rose sharply. The injected chemical solution was 1.5 kg, 2.5 times foamed, and had a compressive strength of 15 MPa.

According to the present invention, a composition for a rock bolt fixing material, a rock bolt fixing material, and a rock bolt fixing material, which are foam type, have less water pollution, have sufficient strength, long-term durability, and a sufficient rate of developing strength, are used. A lock bolt method can be provided.

Claims (4)

A composition for rock bolt fixing material to be placed in the surrounding ground after tunnel excavation.
The composition for the fixing material
It is composed of a component (A) containing a polyol, an amine compound and water (c) and a component (B) containing an isocyanate compound.
The polyol contains a polyether polyol (a1), and is
The amine compounds are diethyltoluenediamine, diethanolamine, 1,2-propanediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, hexamethylenediamine, and terminal aminated propylene glycol (weight average molecular weight less than 2000). It contains at least one amine compound (b1) selected from the group consisting of
A composition for a rock bolt fixing material, wherein the content of the water (c) is 0.3 parts by mass to 2.5 parts by mass with respect to 100 parts by mass of the component (A). The composition for a rock bolt fixing material according to claim 1, wherein the viscosities of the component (A) and the component (B) are both 650 mPa · Sec or less at 25 ° C. A lock bolt fixing material obtained by curing the composition for a lock bolt fixing material according to claim 1 or 2 . A process of drilling multiple holes at predetermined intervals in rock or ground,
The process of inserting a bolt and injection rod with no voids in the hole, and
A rock bolt construction method comprising a step of injecting the composition for a lock bolt fixing material according to claim 1 or 2 into a rock or the ground from the injection rod and solidifying the composition.