Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K17/00—Soil-conditioning materials or soil-stabilising materials
  • C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
  • C09K17/42—Inorganic compounds mixed with organic active ingredients, e.g. accelerators
  • C09K17/46—Inorganic compounds mixed with organic active ingredients, e.g. accelerators the inorganic compound being a water-soluble silicate

Definitions

• the present invention relates to a composition for a rock bolt fixing material and a rock bolt fixing material obtained by curing the composition. More specifically, the present invention relates to a composition for a lock bolt fixing material excellent in long-term durability, which is used in a rock bolt construction method for protecting a tunnel structure, and a lock bolt fixing material obtained by curing the composition.
• the AGF method and the injection-type fore-polling method are methods that stabilize the soil quality at the front upper part to prevent the collapse of the edge during excavation, and ensure the safety from excavation to lining concrete placement.
• the face bolt method is a method for stabilizing the mirror surface, which is the excavation cross section, and the soil in front of the excavation cross section, and ensures safety from completion of excavation in a certain section to the start of the next excavation. These auxiliary methods are intended to improve safety against excavation work.
• the rock bolt method is a method of stabilizing the surrounding natural ground after tunnel excavation, and by fixing the bolt to the natural ground with a fixing material, the ground due to an earthquake etc. together with the lining concrete to be placed afterwards
• the purpose is to protect the tunnel structure from fluctuations. Therefore, high strength and long-term durability are required for the fixing material for fixing the rock bolt to the surrounding ground, ensuring safety when using the tunnel structure. It is very different from the natural cement used in the construction method.
• inorganic materials such as mortar having high strength have been used.
• these inorganic materials have a problem that the work efficiency is not sufficient because of the long time required to develop the strength, and the material flows into the water when water leakage or spring water occurs. It was.
• an organic-inorganic composite material comprising an alkali silicate aqueous solution and an isocyanate compound is used as a fixing material.
• Patent Document 1 an alkali silicate aqueous solution, a water glass component containing a tertiary amine catalyst and glycerin, and an isocyanate component containing diphenylmethane diisocyanate are used as a fixing material composition, so that curing and strength can be achieved in a short time. It is disclosed that it can be expressed.
• compositions for fixing materials have poor compatibility between the water glass component and the isocyanate component, and it is difficult to obtain a uniform cured product.
• amount of glycerin is relatively large, unreacted glycerin tends to remain in the cured product, and there is a concern about water pollution due to elution of these in water.
• the present invention has been made in view of the above problems, suppresses separation of an aqueous silicate solution, is excellent in compatibility between an aqueous silicate solution and an isocyanate component, suppresses elution of an organic compound from a cured product,
• a composition for a lock bolt fixing material that can suppress environmental pollution (particularly water pollution), imparts high strength to a cured product, and is excellent in long-term durability, and a lock bolt fixing material obtained by curing the composition. The purpose is to provide.
• the composition for a rock bolt fixing material of the present invention is a composition for a rock bolt fixing material to be placed in a surrounding natural ground after tunnel excavation,
• the fixing material composition comprises a component (A) containing an aqueous silicate solution and a component (B) containing an isocyanate compound,
• the component (A) is (A1) an aqueous sodium silicate solution, and (A2) containing an amine polyol selected from the group consisting of trialkanolamine and alkyl dialkanolamine,
• the component (B) is (B1) an isocyanate compound, and (B2)
• a rock bolt fixing material composition comprising an ester compound comprising an aliphatic alcohol having 8 to 12 carbon atoms and a polybasic acid.
• the component (A2) is preferably contained in the component (A) in an amount of 0.1 to 5% by weight.
• the component (B1) is A polyisocyanate compound (B11); It is preferably an isocyanate group-terminated urethane prepolymer obtained by reacting a polyether polyol (B12) containing 5 to 50% by weight of an ethylene oxide unit.
• the lock bolt fixing material of the present invention is a lock bolt fixing material obtained by curing a composition for a lock bolt fixing material.
• the composition for a rock bolt fixing material is composed of a component (A) containing an aqueous silicate solution and a component (B) containing an isocyanate compound.
• the component (B) is 30 parts per 100 parts by weight of the component (A). It is preferable that it is blended in an amount of ⁇ 120 parts by weight.
• composition for a rock bolt fixing material of the present invention and the rock bolt fixing material formed by curing the composition, separation of the silicate aqueous solution is suppressed, and the compatibility between the silicate aqueous solution and the isocyanate component is excellent.
• the composition for rock bolt fixing material which can suppress elution of organic compounds from the cured product, can suppress environmental pollution (especially water pollution), imparts high strength to the cured product, and is excellent in long-term durability, and A lock bolt fixing material obtained by curing the composition can be provided.
• the composition for a rock bolt fixing material of the present invention is a composition for a rock bolt fixing material to be cast in a surrounding natural ground after tunnel excavation, and the fixing material composition contains an aqueous silicate solution (A ) Component and (B) component containing an isocyanate compound, and the component (A) is selected from the group consisting of (A1) an aqueous sodium silicate solution and (A2) trialkanolamine and alkyl dialkanolamine. An amine polyol is contained, and the component (B) contains (B1) an isocyanate compound and (B2) an ester compound composed of an aliphatic alcohol having 8 to 12 carbon atoms and a polybasic acid.
• the component (A) containing the silicate aqueous solution contains (A1) an aqueous sodium silicate solution, and (A2) an amine polyol selected from the group consisting of trialkanolamines and alkyl dialkanolamines.
• sodium silicate aqueous solution (A1) a commercially available aqueous solution of sodium silicate can be used as a main component.
• This sodium silicate is represented by the general formula: Na 2 O.xSiO 2 .nH 2 O.
• x represents the molar ratio of SiO 2 (silicon dioxide) to Na 2 O (sodium oxide), and in the present invention, it is 2 to 3, preferably 2.2 to 2.8. If x is smaller than 2, the ratio of the silicic acid gelation reaction in the foam curing reaction is reduced, so that the curability when mixing two components is deteriorated, and if it exceeds 3, the viscosity of the aqueous sodium silicate solution is increased. The mixing property with the later-described component (B) and the workability during use are lowered.
• the solid content concentration of the aqueous sodium silicate solution (A1) is 35 to 50% by weight, preferably 40 to 45% by weight. If the solid content of the aqueous sodium silicate solution is too high, it can be adjusted by diluting with water. If the solid content concentration is less than 35% by weight, the content of water in the mixed liquid when the component (A) and the component (B) are mixed increases, so the compatibility of the two components tends to decrease, If it exceeds 50% by weight, the viscosity of the component (A) becomes too high, so that the miscibility with the component (B) and the workability during use tend to decrease.
• trialkanolamine examples include triethanolamine, tripropanolamine, triisopropanolamine, tributanolamine, and triisobutanolamine. Of these, triethanolamine is preferred from the viewpoint of versatility and economy.
• alkyl dialkanolamine examples include alkyldiethanolamine compounds such as methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, and isopropyldiethanolamine, and alkyldipropanols such as methyldipropanolamine, ethyldipropanolamine, propyldipropanolamine, and isopropyldipropanolamine.
• Alkyl diisopropanolamine compounds such as amine compounds, methyldiisopropanolamine, ethyldiisopropanolamine, propyldiisopropanolamine, isopropyldiisopropanolamine, methyldibutanolamine, ethyldibutanolamine, propyldibutanolamine, isopropyldibutanolamine, etc.
• the blending amount of (A2) is preferably 0.1 to 5.0% by weight, more preferably 0.1 to 2.0% by weight in the component (A).
• the blending amount of (A2) is less than 0.1% by weight, there is a problem that the stabilization effect of the component (A) is insufficient, and foaming and cracking of the cured product due to carbon dioxide cannot be sufficiently suppressed. Even if it exceeds 5.0% by weight, no further effect can be obtained.
• the amine catalyst (A3) can be appropriately blended with the rock bolt fixing material of the present invention.
• the amine catalyst include triethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetra Methylhexamethylenediamine, N, N, N ′, N ′′, N ′′ -pentamethyldiethylenetriamine, N, N, N ′, N ′′, N ′′ -pentamethyldipropylenetriamine, hexamethyltriethylenetetramine, hexamethyltri Propylenetetramine, N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, N, N-dimethylaminopropylamine, tetramethyliminobispropylamine, N, N, N-tris- (3-di
• the blending amount of (A3) can be appropriately adjusted according to the required curing rate, but is preferably 0.1 to 2.0% by weight in the component (A).
• the component (B) contains (B1) an isocyanate compound and (B2) an ester compound composed of an aliphatic alcohol having 8 to 12 carbon atoms and a polybasic acid.
• Examples of (B1) isocyanate compounds include diphenylmethane diisocyanate and its isomers, polymethylene polyphenyl polyisocyanate (polymeric MDI), carbodiimide-modified diphenylmethane diisocyanate, tolylene diisocyanate, crude tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, naphthalene.
• Examples thereof include polyisocyanates such as diisocyanate, hydrogenated diphenylmethane diisocyanate, and trimethylene xylylene diisocyanate alone or as a mixture.
• the isocyanate compound and the polyol compound are such that the equivalent ratio of NCO group to OH group (NCO group / OH group) is in the range of 1.5 to 300, preferably 2.0 to 100.
• An isocyanate group-terminated urethane prepolymer obtained by reacting by a known method can also be used.
• polyol compounds include diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexanediol.
• triol compounds such as glycerin, trimethylolpropane, other polyols such as pentaerythritol, sorbitol, sucrose, monoethanolamine, diethanolamine, triethanolamine, and alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide
• polyether polyol formed is mentioned.
• it is excellent in compatibility with sodium silicate (A1) and the two-component mixed solution can further suppress wastewater contamination when water contacts before curing, it contains 5 to 50% by weight of ethylene oxide units.
• Polyether polyols are preferred.
• polymeric MDI is extremely low in volatility under the handling environment temperature, has a flash point of 200 ° C. or higher, is liquid, and has an economical structure.
• an isocyanate group-terminated urethane prepolymer using the same is preferred, and an isocyanate group-terminated urethane prepolymer is more preferred.
• the blending amount of (B1) is 50 to 95% by weight in the component (B). By making it within the above range, (B1) an isocyanate group in the isocyanate compound and (A1) water in the sodium silicate aqueous solution react to form sufficient strength to the cured product by the urea bond formed. become able to.
• the compatibility of the component (A) and the component (B) can be improved, and (B1) foaming of a cured product by carbon dioxide generated by the reaction between the isocyanate compound and water. It can suppress and can give sufficient intensity
• polybasic acid examples include dibasic acids such as adipic acid, azelaic acid, sebacic acid and phthalic acid, tribasic acids such as trimellitic acid, and tetrabasic acids such as pyromellitic acid. Since the component (B) can have a lower viscosity, a dibasic acid is preferable. Moreover, adipic acid which can reduce water pollution from a viewpoint of environmental influence is more preferable.
• the aliphatic alcohol having 8 to 12 carbon atoms include octyl alcohol, nonyl alcohol, isononyl alcohol, decyl alcohol, isodecyl alcohol, undecyl alcohol, and dodecyl alcohol.
• the blending amount of (B2) is preferably 1 to 50% by weight, more preferably 3 to 30% by weight in the component (B). By setting it within the above range, the viscosity of the component (B) can be reduced, and good curability and strength can be imparted.
• the rock bolt fixing material of the present invention is a rock bolt fixing material obtained by curing the composition for a rock bolt fixing material.
• the blending amount of the component (A) and the component (B) in the rock bolt fixing material composition is preferably 30 to 120 parts by weight of the component (B) with respect to 100 parts by weight of the component (A). More preferred are parts by weight. If it is less than the above range, poor curing is likely to occur, and if it is more than the above range, the amount of carbon dioxide generated at the time of curing increases, so that the foaming ratio of the lock bolt fixing material increases or cracks occur in the lock bolt fixing material. It becomes easy and it may become difficult to obtain sufficient strength.
• the time from the start of mixing of component (A) and component (B) to curing is preferably 30 to 180 seconds when the components (A) and (B) are mixed at a liquid temperature of 20 ° C. If the length is shorter than the above range, there is a possibility that the lock bolt tip cannot be sufficiently filled.
• the lock bolt fixing material of the present invention has a 50% compressive strength of 20 MPa or more, preferably 30 MPa or more, measured according to JIS K 7220 (Compression test method for hard foamed plastic). Preferably there is.
• the lock bolt fixing material of the present invention preferably has a bending strength measured according to JIS K 7221 (bending test method of hard foamed plastic) of 5 MPa or more, preferably 10 MPa or more. .
• the foaming ratio of the rock bolt fixing material is preferably low.
• the foaming ratio when the component (A) and the component (B) are mixed at a liquid temperature of 20 ° C. is preferably 1 to 3 times, more preferably 1 to 2 times.
• the ratio is more preferably 1.5 times, and most preferably 1 to 1.3 times.
• the amount of organic matter contained in water after being immersed in water at a liquid temperature of 20 ° C. for 7 days is in accordance with JIS K 0102 (Industrial Wastewater Test Method).
• the measured potassium permanganate consumption is preferably 10 mg / L or less.
• AI to A-IX were prepared by blending the following raw materials in the blending ratio shown in Table 1.
• Sodium silicate 1 SiO 2 / Na 2 O ratio 2.2 (molar ratio), solid content 41 wt%
• Sodium silicate 2 SiO 2 / Na 2 O ratio 2.5 (molar ratio)
• solid content 40% by weight
• Sodium silicate 3 SiO 2 / Na 2 O ratio 2.9 (molar ratio)
• Amine polyol 1 Triethanolamine
• Amine polyol 2 N-methyldiethanolamine
• Polyol 1 Glycerine
• Amine catalyst 1 Triethylenediamine Amine catalyst 2: N, N, N'-trimethylaminoethylethanolamine
• BI to B-IX were prepared by blending the following raw materials in the blending ratio shown in Table 2.
• PP-1 polyether obtained by block addition polymerization of 75 parts by weight of polymeric MDI (trade name: Coronate 1106, manufactured by Nippon Polyurethane) and 70% by weight of propylene oxide and 30% by weight of ethylene oxide on glycerin
• An isocyanate group-terminated urethane prepolymer PP-1 (NCO content: 25 wt%) was obtained by reacting 15 parts by weight of a polyol (number average molecular weight 1500) at 80 ° C. for 3 hours.
• PP-2 Polymeric MDI (trade name: Foamlite NE5000B, manufactured by BASF Inoac Polyurethane) 75 parts by weight, obtained by block addition polymerization of propylene oxide 68% by weight and ethylene oxide 32% by weight to glycerin By reacting 15 parts by weight of a polyether polyol (number average molecular weight 1500) at 80 ° C. for 3 hours, an isocyanate group-terminated urethane prepolymer PP-2 (NCO content 25% by weight) was obtained.
• a polyether polyol number average molecular weight 1500
• PP-3 Polymeric MDI (trade name: Cosmonate M-50, manufactured by Mitsui Chemicals) 80 parts by weight, obtained by block addition polymerization of propylene glycol 75% by weight and ethylene oxide 25% by weight By reacting 20 parts by weight of the obtained polyether polyol (number average molecular weight 1000) at 80 ° C. for 3 hours, an isocyanate group-terminated urethane prepolymer PP-3 (NCO content 26% by weight) was obtained.
• Ester compound 1 Diisononyl adipate
• Ester compound 2 Dioctyl adipate
• Ester compound 3 Diisodecyl adipate
• PC Propylene carbonate
• DBA Dibutyl adipate
• Flash point The flash point was measured according to the Cleveland open type. The results are shown in Table 2. Those with a flash point of 200 ° C or higher fall under the Fire Service Act Dangerous Goods Class 4 and 4 petroleum, and those with a flash point of less than 200 ° C and 70 ° C or higher fall under the Fire Services Act Dangerous Goods Class 4 and 3rd petroleum. As shown in Table 2, it can be seen that B-VIII and B-IX have a low flash point of 200 ° C. or lower and high flammability.
• Examples 1 to 12 and Comparative Examples 1 to 5 The components (A) and (B) whose temperature was adjusted to 20 ° C. were weighed into a 300 mL capacity polycup in the combinations and blending ratios (weight ratios) shown in Tables 3 and 4, and 10 times at a rotation speed of 500 rpm with a mixer.
• the rock bolt fixing material was obtained by mixing, stirring and curing for 2 seconds. The following evaluation was performed about the property at this time. The results are shown in Table 3.
• the liquid mixture mixed by the above method was quickly poured into a cylindrical mold having a diameter of 5 ⁇ 10 cm, allowed to stand at 20 ° C. for 24 hours, and then taken out from the mold to prepare a specimen. After immersing this specimen in 10 L of distilled water and allowing it to stand at 20 ° C. for 7 days, the amount of organic matter contained in the sample water was determined as potassium permanganate consumption according to JIS K 0102 (industrial wastewater test method). It was measured.
• Comparative Example 1 As shown in Tables 3 and 4, it was found that in Comparative Example 1 containing no amine polyol, the compatibility of the components (A) and (B) was poor, and a uniform rock bolt fixing material could not be obtained. It was. Further, it was found that the lock bolt fixing material was easily foamed and sufficient strength could not be obtained. In Comparative Example 2 in which glycerin was used in place of the amine polyol, it was found that the compatibility of the components (A) and (B) was poor and a uniform rock bolt fixing material could not be obtained. Further, it has been found that the lock bolt fixing material tends to foam and sufficient strength cannot be obtained. It was also found that the amount of organic matter elution was increased.
• Comparative Example 3 in which glycerin was used in a larger amount than Comparative Example 2, it was found that the compatibility between the component (A) and the component (B) was poor, and a uniform rock bolt fixing material could not be obtained. Further, it was found that the lock bolt fixing material was more easily foamed than Comparative Examples 1 and 2, and sufficient strength could not be obtained. Furthermore, it was found that the amount of organic matter elution was further increased as compared with Comparative Examples 1 and 2. In Comparative Example 4 using propylene carbonate instead of the ester compounds 1 to 3 of the present invention, the lock bolt fixing material is much more easily foamed than Comparative Examples 1 and 2, and sufficient strength cannot be obtained. I understood.

Landscapes

• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Soil Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)
• Soil Conditioners And Soil-Stabilizing Materials (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=43544064

Family Applications (1)

Country Status (3)

Cited By (1)

Families Citing this family (1)

Citations (5)

• 2009
  • 2009-08-07 JP JP2009184499A patent/JP5475362B2/ja active Active
  • 2009-10-28 WO PCT/JP2009/068473 patent/WO2011016149A1/ja active Application Filing
  • 2009-11-03 TW TW98137188A patent/TWI395805B/zh active

Patent Citations (5)

Also Published As

Similar Documents

Legal Events