JP2019059942A - Composition for rock bolt anchoring material, rock bolt anchoring material and rock bolt method - Google Patents

Abstract

To provide a composition for rock bolt anchoring material that is of a foaming type but causes less contamination of water quality, and has sufficient strength, long-term durability, and sufficient strength development rate, and a rock bolt anchoring material obtained by curing the composition.SOLUTION: The present invention provides a composition for rock bolt anchoring material for pouring around natural ground after tunneling. The composition contains (A) component containing a polyol, an amine compound and water (c), and (B) component containing an isocyanate compound. The polyol contains a polyetherpolyol (a1). The amine compound contains an amine compound (b1) having a primary or secondary amino group. The content of the water (c) is 0.3 pt.mass-2.5 pts.mass relative to the (A) component 100 pts.mass.SELECTED DRAWING: None

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 for enhancing safety during excavation such as AGF method, injection type fore polling method, face bolt method, etc., and rock bolt method for suppressing deformation of tunnel after excavation etc. Two types of construction methods are adopted.

  The AGF construction method and the pouring type fore polling method are methods for stabilizing the soil quality at the upper front in order to prevent the falling edge at the time of excavation, and secure the safety from excavation to lining concrete placement . The face bolt method is a method for stabilizing the mirror surface which is the excavated cross section and the soil quality in front of it, and secures the safety from the completion of the excavation of a certain section to the start of the next excavation. These auxiliary construction methods are aimed at improving the safety of drilling operations.

  The rock bolt method is a method to stabilize the surrounding ground after tunnel excavation, and by fixing the bolts to the ground with a fixing material, the ground movement due to the earthquake etc. along with the lining concrete to be installed after that The purpose is to protect tunnel structures. Therefore, the fixing material for fixing the lock bolt to the surrounding ground is required to have high strength and long-term durability for securing safety at the time of using the tunnel structure. It is very different from the ground cement used in the construction method.

  Conventionally, inorganic materials such as mortar having high strength have been used as such lock bolt fixing materials. However, these inorganic materials do not have sufficient working efficiency because the time required for strength development is long, and there is a problem that the materials will flow out into water if water leakage or spring water occurs. The

  Then, in order to solve these problems, the organic-inorganic composite material which consists of alkali-silicate aqueous solution and an isocyanate compound is used as a fixing material (refer patent document 1 and 2).

JP, 2002-285155, A JP, 2011-37946, A

  However, the fixing material of Patent Document 1 has problems of long-term durability and water pollution. In recent years, there has also been a demand for a foam-type fixing material capable of easily filling the gap between the rock bolt and the surrounding ground in view of the demand for cost reduction and the improvement of the fixing performance of 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 foamed type, composition for rock bolt fixing material having sufficient strength, long-term durability, and sufficient strength development speed with little water pollution, and the same An object of the present invention is to provide a lock bolt fixing material in which a composition is cured.

  As a result of intensive studies, the inventors of the present invention have used a liquid chemical composition comprising (A) component comprising a predetermined polyol and a predetermined amine compound and (B) component comprising an isocyanate compound, It discovered that the said subject could be solved and repeated examination, and completed this invention.

That is, the present invention
[1] A composition for a rock bolt fixing material to be placed in a surrounding ground after tunnel excavation, wherein the fixing material composition comprises a polyol, an amine compound and water (c). And a component (B) comprising an isocyanate compound, wherein the polyol contains a polyether polyol (a1), and the amine compound has an amine compound having a primary or secondary amino group (b1) Containing
The composition for a lock 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 lock bolt fixing material according to the above [1], wherein the polyol further contains a castor oil-based polyester polyol (a2),
[3] For the lock bolt fixing material according to the above [2], wherein the content ratio [(a1) / (a2)] of the polyether polyol (a1) to the castor oil-based polyester polyol (a2) is 1.3 or more Composition,
[4] The amine compound (b1) having a primary or secondary amino group is diethyltoluenediamine, diethanolamine, 1,2-propanediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, hexamethylenediamine And the composition for lockbolt fixing material according to any one of the above [1] to [3], which is at least one compound selected from the group consisting of terminal aminated propylene glycol (weight average molecular weight less than 2000) ,
[5] The lock bolt fixing material according to any one of the above [1] to [4], wherein the viscosity of each of the components (A) and (B) is 650 mPa · Sec or less at 25 ° C. Composition,
[6] A lock bolt fixing material obtained by curing the composition for a lock bolt fixing material according to any one of the above [1] to [5],
[7] A process of drilling a plurality of holes at a predetermined interval in a rock or ground, a process of inserting a bolt and an injection rod without an air gap in the holes, and the process of the above-mentioned [1] to [5]. A rock bolt construction method comprising the steps of: injecting the composition for a rock bolt fixing material according to any one of the above into a rock or ground and solidifying it.
About.

  According to the present invention, a composition for a rock bolt fixing material having a sufficient strength, long-term durability, and a sufficient strength development rate with little water contamination, despite being a foam type, and a lock bolt formed by curing the composition Fixing material can be provided.

  Moreover, if a castor oil-based polyester polyol (a2) is added to the component (A), the expansion ratio can be more suitably controlled, which is preferable.

  The respective elements constituting the present invention will be described below.

<(A) component>
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 may further 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 can further contain a tertiary amine compound (b2).

(Polyether polyol (a1))
The polyether polyol (a1) used in the present invention is not particularly limited, and examples thereof include monools such as methanol, ethanol, propanol, butanol, octanol and lauryl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Diols such as dipropylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and polyols such as glycerin, trimethylolpropane and pentaerythritol; other monoethanolamines and diethanolamines Ethylene oxide, propylene oxide, and mixtures thereof with an active hydrogen-containing compound such as triethanolamine, diglycerin, sorbitol, sucrose, etc. N'okishido, butylene oxide, an alkylene oxide such as styrene oxide using one or more include monools or polyols obtained by addition polymerization by a known method.

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

  Among these, polyether polyols obtained by addition polymerization of propylene oxide to glycerin, polyether polyols obtained by propylene oxide addition polymerization to propylene glycol, polyether polyols obtained by propylene oxide addition polymerization to sorbitol are preferable.

  In these polyether polyols (a1), the weight average molecular weight (Mw) is preferably 800 or less, more preferably 650 or less, from the viewpoint of workability and maintaining the compressive strength of the cured product. More preferably, it is 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 Corp. is used as a GPC main body, column temperature 40 ° C., pump flow rate 0.6 to 1.0 ml / min, RI as a detector (built in GPC main body Column: TSKgel G6000H HR + G4000H HR + G3000H HR + G2000H HR (used in four lines); Mobile phase: THF; Injection volume: 80 μl; Sample concentration: 0 .2% (w / v)]. In this method, for example, the molecular weight can be determined as a PPG equivalent molecular weight using a calibration curve (calibration with a molecular weight of 250 or more) of a standard PPG whose molecular weight is known in advance.

  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 polyols (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, and more preferably 55 to 90% by mass, with respect to 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 lock 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 hydrogenated to castor oil, or hydrogenated castor oil fatty acid hydrogenated to castor oil fatty acid Polyol. Such castor oil-based polyester polyols (a2) include castor oil, transesterified product of castor oil with other natural fats and oils, reaction product of castor oil with polyhydric alcohol, castor oil with fatty acid and polyhydric alcohol Esterification product, hydrogenated castor oil, transesterified product 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 And a polyol obtained by addition polymerization of an alkylene oxide thereto. Of these, castor oil is most preferred.

  In the present invention, by using these castor oil-based polyester polyols (a2), the expansion ratio of the lock bolt fixing material does not become excessively large, and therefore, the environment when the cured product flows out due to water leakage or spring water. It is possible to obtain a sufficient strength, long-term durability, and a sufficient strength development rate, with little adverse effect on the quality.

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

  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 polyols (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, and more preferably 10 to 30% by mass, with respect to 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 such that (a1) / (a2) is 1.3 or more, more preferably 1.5 or more, and further preferably Is 3.5 or more. 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. The term "about" in this case is intended to allow a variation of about ± 0.1.

(Amine compound (b1))
The amine compound (b1) having a primary or secondary amino group to be used in the present invention is not particularly limited, and examples thereof include monomethylamine, monoethylamine, monobutylamine, dimethylamine, diethylamine, din-propylamine and diisopropyl ester. Alkyl monoamines such as amine, dibutylamine, diamylamine, dihexylamine, methylethylamine, methylpropylamine, methylisopropylamine, ethylpropylamine, ethylisopropylamine, N-methyldodecylamine, bis (2-ethylhexyl) amine; monoethanolamine , Alkanol monoamines such as diethanolamine and diisopropanolamine; cyclopentylamine, cyclohexylamine, N-methylcyclohexylamine, N-ethyl Alicyclic monoamines such as clohexylamine or dicyclohexylamine; aromatic monoamines such as N-methylbenzylamine, dibenzylamine, benzylamine, p-methylbenzylamine; and heterocycles such as morpholine, pyrrolidine, piperidine or 1H pyrazole Formulas: monoamines; hydrazines; aliphatic diamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, neopentanediamine and the like; -Diaminocyclohexylmethane, isophoronediamine, bisaminomethylcyclohexane, 2,5- or 2,6-diaminomethylbicyclo [2,2,1] heptane, diaminocyclohexane, diethyl Alicyclic diamines such as luene diamine; aromatics such as diaminodiphenylmethane, diaminodiphenylether, xylylenediamine, phenylenediamine, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene Diamines; aliphatic triamines such as diethylenetriamine; aromatic or alicyclic triamines such as 1,3,5-tris (aminomethyl) benzene and 1,3,5-tris (aminomethyl) cyclohexane; water, ethylene glycol, propylene Polyoxyalkylene diamine obtained by converting hydroxyl group of polyoxyalkylene glycols obtained by addition polymerization of propylene oxide and / or ethylene oxide to glycol etc. to amino group; Propylene such as glycerin, trimethylolpropane etc. The polyoxyalkylene triamine etc. which are obtained by converting the hydroxyl group of polyoxyalkylene triols obtained by addition-polymerizing ethylene oxide and / or ethylene oxide into an amino group etc. are mentioned.

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

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

  The content of the amine compound (b1) is preferably 2 to 12% by mass, and more preferably 3 to 10% by mass, with respect to the total amount of the component (A). If it is less than 2% by mass, it will tend to be difficult to suppress white turbidity, and if it is more than 12% by mass, the load applied to the mixer bolt etc. at the time of construction tends to be large.

(Tertiary amine compound (b2))
In the present invention, as the tertiary amine compound (b2), known compounds can be used without particular limitation, and examples thereof include 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 Aminopropyl imidazole, hexamethyltriethylenetetramine, hexa Tilt polypropylene tetramine, N, N, etc. N- tris (3-dimethylaminopropyl) amine.

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

  0.3-10 mass% is preferable with respect to the total amount of (A) component, and, as for content of a tertiary amine catalyst (b2), 0.5-7 mass% is more preferable. If it is less than 0.3% by mass, the workability tends to deteriorate, and if it is more than 10% by mass, the load applied to the mixer bolt or the like at the time of construction tends to be large.

  Content of the water (c) used for this invention is 0.3 mass part-2.5 mass parts with respect to 100 mass parts of said (A) components. Preferably, it is 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, adverse effects on the environment when the cured product flows out due to water leakage or spring water can be reduced, and sufficient strength, long-term durability, and sufficient strength development speed can be obtained.

(Other ingredients)
In the component (A) according to the present invention, in addition to the above-mentioned components, if necessary, such as silicon-based foam stabilizer, diluent, flame retardant, pigment, inorganic filler, crosslinking agent, coupling agent, etc. Known additives can be added within the range that does not impair the object of the present invention.

  Although it does not specifically limit as a silicone type foam stabilizer, For example, the polyoxyalkylene dimethylpolysiloxane copolymer normally used to hard foaming urethane resin is mention | raise | lifted.

  The diluent is not particularly limited, and examples thereof include phthalic acid esters such as dibutyl phthalate, dioctyl phthalate and diisononyl phthalate, dibutyl adipate, dioctyl adipate, diisononyl adipate, and bis (2- (2-butoxyethoxy) ethyl) adipate. There may be mentioned trimellitic acid esters such as adipic acid esters and tri (2-ethylhexyl) trimellitate. Among these, bis (2- (2-butoxyethoxy) ethyl) adipate and tri (2-ethylhexyl) trimellitate are preferable because they have little impact on the environment and are excellent in safety.

  Although it does not specifically limit as a flame retardant, For example, any of an addition type and a reaction type can be used. Specific examples of the additive type include phosphorus-containing halogen-containing systems such as tributyl phosphate, tricresyl phosphate, tris monochloroisopropyl phosphate and the like; halogen-containing systems such as chlorinated paraffin, pentabromoethylbenzene, decabromodiphenyl ether etc. can give. Specific examples of the reactive type include, for example, halogen-containing phosphorus-containing compounds having a hydroxyl group or an amino group such as dibromoneopentyl glycol, tetrabromobisphenol A, diethyl N, N-dihydroxyethylaminomethyl phosphotate, various phosphorus-containing polyols, etc. Etc.

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

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

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

(Isocyanate compound)
The isocyanate compound is not particularly limited. For example, diphenylmethane diisocyanate and its isomer, polymethylene polyphenyl polyisocyanate (polymeric MDI), tolylene diisocyanate, crude tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, naphthalene diisocyanate, water Diphenylmethane diisocyanate, polyisocyanates such as trimethylene xylylene diisocyanate, alone or in mixtures; carbodiimide-modified products of these polyisocyanates, or those obtained by adding a catalyst to form dimers or trimers: the above-mentioned polyethers An isocyanate obtained by reacting with a polyol (a1) or a castor oil-based polyester polyol (a2) Etc. alone or a mixture of group-terminated urethane prepolymer and the like.

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

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

(Other ingredients)
The conventionally known additives described in the section of the component (A) can be added to the component (B) according to the present invention, as necessary, as long as the object of the present invention is not impaired. .

(viscosity)
In the present invention, from the viewpoint of workability, the viscosity of the component (B) is preferably 650 mPa · sec or less at 25 ° C., more preferably 600 mPa · sec or less, and still more preferably 450 mPa · sec or less. 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 component (A) to component (B) according to the present invention is the reaction equivalent ratio of the OH group and NH ₂ group of the polyol in component (A) to the NCO group in component (B), ie, It is preferable that (OH + NH ₂ ) / NCO is in the range of 1/5 to 5/1, and 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 longer, and the lock bolt fixing is performed. The strength of the material tends to be small and brittle.

(Gel time)
It is preferable that the gel time at the time of mixing the (A) component and (B) component which were adjusted to 20 degreeC, respectively is 25 to 55 seconds for the composition for lock bolt fixing materials of this invention. When the gel time is less than 25 seconds, the workability tends to deteriorate, while when it is more than 55 seconds, the clouding tends to occur, which is not preferable. Here, gel time is the time until gelation occurs when mixing by hand mixing after the component (A) and component (B) each having a total amount of 30 g is adjusted to 20 ° C. (that is, curing proceeds and stringing occurs) Say the time when

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

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

(PH)
In the present invention, after mixing the (A) component and the (B) component, the mixture is poured into 10 volumes of water, and after completion of the reaction, the pH measured by collecting the supernatant is 5-9. Is preferred.

<Lock bolt method>
The composition for a lock bolt fixing material and the lock bolt fixing material of the present invention are used as a fixing material when fixing a bolt to a ground, for example, in a lock bolt method for stabilizing the surrounding ground after tunnel excavation. . The fixation of the porto can protect the tunnel structure from ground movement due to an earthquake or the like together with lining concrete that is subsequently installed.

  There is no particular limitation on the method of injecting and solidifying the fixing material, and a known method may be adopted, but a step of drilling a plurality of holes at a predetermined interval in the ground, inserting a lock bolt in the holes It is preferable that the process comprises the steps of: injecting the composition for lock bolt fixing material into the ground and solidifying.

  The step of injecting into the ground and solidifying it is, for example, a method using a comparative compounding pump capable of controlling the injection amount, pressure and compounding ratio of the (A) component and the (B) component, for example. There is. In this method, the (A) component and the (B) component are put in separate tanks and fixed in advance to a predetermined place such as a rock (for example, a plurality of holes drilled at intervals of about 0.5 to 3 m) Each component in the tank is injected at an injection pressure of 0.05 to 25 MPa through an injection rod having the static mixer and check valve etc. inserted therein, and a predetermined amount of (A) component and The components (B) are mixed uniformly, poured into the ground and consolidated.

  For example, when injecting into the top of a tunnel, prior to injection, for example, about 1 m in the excavating direction, although not specifically limited in the cross sectional direction, for example, a leg of 42 mmφ at a predetermined interval according to the ground A hole is drilled using an auger, an injection hole with a depth of 3 m and a drilling angle of 90 ° is provided, and a lock bolt with a length of 3 m, in which a static mixer and a check valve are installed, is inserted into the injection hole. In order to prevent the backflow of the injected chemical solution, it is preferable to seal the mouth of the lock bolt with a rag and 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 it is increased by about 50% more than the predetermined injection amount. In general, it is preferable to infuse 0.5 to 5.0 kg of chemical solution per injection hole.

  Although the present invention will be described in detail based on examples, the present invention is not limited to these.

Raw materials used
(Polyether polyol (a1))
Polyol (a1-1): Polyether polyol having an average hydroxyl value of 480 mg KOH / g obtained by addition polymerization of propylene oxide to glycerin (trade name: DK Polyol G 480, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
Polyol (a1-2): Polyether polyol having an average hydroxyl value of 280 mg KOH / g, obtained by propylene oxide addition polymerization to propylene glycol (trade name: Hiflex D400, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
Polyol (a1-3): Polyether polyol having an average hydroxyl value of 550 mg KOH / g obtained by addition polymerization of propylene oxide to sorbitol (trade name: Exenol 550 SO, manufactured by Asahi Glass Co., Ltd.)
Polyol (a1-4): Polyether polyol having an average hydroxyl value of 56 mg KOH / g, obtained by propylene oxide addition polymerization to glycerin (trade name: Hiflex G 3000 C, 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.)
Polyol (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.)
Polyol (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.)
Polyol (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.)
Polyol (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 primary or secondary amino group (b1))
Amine compound (b1-1): diethyltoluenediamine (trade name: DETDA 80, 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): hexamethylene diamine (manufactured by Nacalai Tesque, Inc.)
Amine compound (b1-6): terminal aminated polypropylene glycol (trade name: Jeffamine D-2000, manufactured by Huntsman)

(Amine compound having 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: Foamlight 200B, manufactured by BASF INOAC polyurethane)
Isocyanate compound 2: Polymeric MDI (trade name: Foamlight 500B, manufactured by BASF INOAC polyurethane)

<Preparation of agent A and agent B>
The agent A and the agent B were respectively prepared by using the solution consisting of the component (A) as the agent A and the solution consisting of the component (B) as the agent B and appropriately mixing the materials according to the formulation described in Table 1.

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

<Evaluation of cured product>
(Gel time)
The agent A and the agent B prepared according to the formulation described in Table 1 were separately prepared so as to be 30 g in total at the mixing ratio described in Table 1. After setting the temperatures of both the agent A and the agent B to 20 ° C., the agent A and the agent B were mixed by hand mixing, and gel time (time for curing to proceed and stringing to start) was measured.

(Foaming reactivity, foaming ratio)
The agent A and the agent B prepared according to the formulation described in Table 1 were separately prepared so as to be 30 g in total at the mixing ratio described in Table 1. After the temperatures of the agent A and agent B were both set to 20 ° C., the agent A and agent B were mixed by hand mixing, and the foaming start time and the 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 agent A and the agent B as raw materials.

(Compression strength)
The agent A and the agent B prepared according to the formulation described in Table 1 were separately prepared so as to be 30 g in total at the mixing ratio described in Table 1. After setting the temperature of both the agent A and the agent B to 20 ° C., the agent A and the agent B were mixed by hand mixing to obtain a cured product. From the cured product, a test piece of 10 mm × 10 mm × 10 mm was cut out and measured by an Instron universal tester according to JIS A 9511.

<Water turbidity test>
The agent A and the agent B prepared according to the formulation described in Table 1 were separately prepared so as to be 30 g in total at the mixing ratio described in Table 1. Both the agent A and the agent B were brought to 20 ° C., and then the prepared agent A and agent B were mixed by hand mixing for 10 seconds, and then the mixture was immediately charged into a container containing 300 g of water. The container was capped, and 30 seconds after the start of mixing of the agent A and the agent B, the whole container was vigorously shaken up and down and continued for 10 seconds. After foaming is completed, water is collected from the container, and the turbidity of the water is measured by visual observation and spectrophotometer (manufactured by Hitachi Spectrophotometer U-3900H (manufactured by Hitachi High-Technologies Corporation)) light transmittance at 500 nm (% It measured by). The transmittance is preferably 50% or more.

  The results are shown in Table 1.

<Example of experiment>
A rock bolt with a length of 3 m and a static mixer and a check valve installed inside a 3 m deep injection hole with a drilling angle of 90 ° drilled using a 42 mm diameter leg auger in the top of the tunnel And the formulation of Example 1 was infused until the infusion pressure rose sharply. The injected chemical solution was 1.5 kg, 2.5 times foam, and the compressive strength was 15 MPa.

According to the present invention, a composition for a rock bolt fixing material, a rock bolt fixing material, and a foamed bolt type having little water pollution, sufficient strength, long-term durability, and sufficient strength developing speed We can provide the lock bolt method.

Claims (7)

It is a composition for rock bolt fixing material to be installed in the surrounding ground after tunneling.
The fixing material composition is
A component (A) comprising a polyol, an amine compound and water (c) and a component (B) comprising an isocyanate compound,
The polyol contains a polyether polyol (a1),
The amine compound contains an amine compound (b1) having a primary or secondary amino group,
The composition for lock bolt fixing materials whose content of the said water (c) is 0.3 mass part-2.5 mass parts with respect to 100 mass parts of said (A) components.   The composition for a rock bolt fixing material according to claim 1, wherein the polyol further contains a castor oil-based polyester polyol (a2).   The composition for a lock bolt fixing material according to claim 2, wherein the content ratio [(a1) / (a2)] of the polyether polyol (a1) to the castor oil-based polyester polyol (a2) is 1.3 or more.   The amine compound (b1) having a primary or secondary amino group is diethyltoluenediamine, diethanolamine, 1,2-propanediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, hexamethylenediamine, and a terminal The composition for Rockbolt fixing material according to any one of claims 1 to 3, which is at least one compound selected from the group consisting of aminated propylene glycol (weight average molecular weight less than 2000).   The composition for a lock bolt fixing material according to any one of claims 1 to 4, wherein the viscosity of each of the component (A) and the component (B) is 650 mPa · Sec or less at 25 ° C.   The lock bolt fixing material obtained by hardening the composition for lock bolt fixing materials of any one of Claims 1-5. Drilling a plurality of holes in the rock or ground at predetermined intervals;
Inserting a bolt and injection rod without a void in the hole;
The rock bolt construction method comprising the step of injecting the composition for a rock bolt fixing material according to any one of claims 1 to 5 into a rock or ground from the injection rod and consolidating.