KR100220651B1 - Curable composition and method of construction for stabilization of ground - Google Patents

Abstract

One or two or more inorganic compounds selected from the group consisting of hydroxides, oxides, carbonates, sulfates, nitrates, aluminates, borates and phosphates of metals selected from the group consisting of lithium, sodium, boron and aluminum, water and isocyanates The curable composition which consists of these, and the curable composition which contains a polyol, a foam stabilizer, a reaction catalyst, a solvent, surfactant, a deodorant, and a flame retardant as needed in this curable composition are disclosed.

In addition, there is disclosed a ground stabilization method consisting of injecting the curable composition into a soft ground.

Description

Curable composition and ground stabilization method using the same

The present invention relates to, for example, a curable composition to be injected into a soft ground, a cavity of a rock, and a gap such as acid and concrete segments, and a ground stabilization method using the same.

Conventionally, various chemical liquids have been proposed as inorganic liquids such as water glass, fast cement, and organic compounds such as acrylamide and urethane, which are injected into the soft ground around them when excavating tunnels. (From investigation design to construction of chemical injection method, published in October of the Soil Engineering Society, Pyeongseong Won; New technology of mountain tunnel, history of civil engineering, November 3, Pyeongseong).

However, although the inorganic chemicals are excellent in terms of stability, the initial strength of the cured product is low, and the subsequent strength development takes time, and the organic chemicals are obtained with high initial strengths. The performance which satisfies all the conditions required in the ground stabilization construction work that there is once and for all, and the stable strength expression is obtained over the initial stage and the long term, and there is no environmental pollution is obtained What is not lost is the current state.

On the other hand, in general, the most feared ground stabilization work in a closed place such as a tunnel is the mine fire.

Inorganic chemicals do not have any problems with such a fire, but problems such as the long-term suspension of construction work on site are required because the injection method requires a lot of trouble, the curing time after injection is long, and the generation of strength takes time. As a improvement of this, a two-component urethane chemical solution of a polyol liquid and an isocyanate liquid has been proposed (Japanese Patent Laid-Open No. 63-8477).

This two-component urethane-based chemical is known as an extremely excellent rock hardening chemical that has a short curing time, easy injection construction, and does not interfere with construction progress too much.

However, in the urethane-based chemical liquid, the main component of which polyhydric alcohol and isocyanate react to form a polyurethane bubble as a cured product is an organic material, and when a hardening material occurs, the cured product burns at the same time, which may worsen the situation. there was.

In addition, polyurethane is an expensive resin, and it is economically impractical to inject it in the ground in large quantities.

MEANS TO SOLVE THE PROBLEM As a result of various examinations, the present inventors acquired the knowledge that the problem which the said inorganic chemical | medical agent and organic chemical | medical solution have been solved by using a specific material came to complete this invention.

That is, the present invention is one, selected from the group consisting of hydroxides, oxides, carbonates, sulfates, nitrates, aluminates, borates, and phosphates of metals selected from the group consisting of lithium, sodium, potassium, boron, and aluminum, or A curable composition comprising two or more inorganic compounds, water and isocyanates, and again, a curable composition containing one or two or more selected from the group consisting of polyols, foam stabilizers, and reaction catalysts, and cured compositions and solvents thereof. And / or a curable composition containing a surfactant, and again, a curable composition containing these curable compositions, a deodorant and / or a flame retardant, and is a ground stabilizing method characterized by being injected using the same.

Hereinafter, the present invention will be described in detail.

In the present invention, usually one selected from the group consisting of hydroxides, oxides, carbonates, sulfates, nitrates, aluminates, borates and phosphates of metals selected from the group consisting of lithium, sodium, potassium, boron, and aluminum or A liquid containing an aqueous solution or slurry of two or more inorganic compounds and a liquid B containing isocyanates are used.

Solution A and solution B solidify upon contact. For example, when used in the ground, when the liquid A and the liquid B come into contact with each other, the curing reaction occurs quickly, for example, within 5 minutes, and a solid flame-retardant cured product is formed in the ground to stabilize the soft ground.

In particular, since the hardened | cured material formed in the ground by this reaction is flame-retardant, a problem is hardly found also about a hardening material.

Inorganic compounds (hereinafter referred to as inorganic matters) used in the present invention include hydroxides, oxides, carbonates, sulfates, nitrates, aluminates, borates, and phosphates of metals selected from the group consisting of lithium, sodium, potassium, boron, and aluminum. There is one or two or more selected from the group consisting of.

Specifically, lithium hydroxide, sodium hydroxide, potassium hydroxide, and aluminum hydroxide as hydroxide, sodium oxide, potassium oxide, boron oxide and aluminum oxide as oxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium carbonate, hydrogen carbonate as carbonate Sodium and potassium hydrogen carbonate, sodium sulfate, potassium sulfate, aluminum sulfate, sodium hydrogen sulfate, sodium hydrogen sulfate, and sodium hydrogen sulfate, nitrate, sodium nitrate, potassium nitrate, aluminate, sodium aluminate and potassium aluminate, Examples of the borate salts include sodium borate and sodium phosphate, sodium phosphate, sodium tripolyphosphate, and the like.

Moreover, these double salts, complex salts, and clay minerals can also be used in the present invention.

Among these, the use of lithium carbonate, sodium carbonate, potassium carbonate, sodium aluminate, potassium aluminate and sodium borate is preferable, and among them, the use of potassium carbonate is more preferable in view of solubility, workability and economy.

In addition, inorganic salts such as hydroxides, oxides, and carbonates of lithium, sodium, potassium, boron, and aluminum are generally aqueous solutions in terms of dissolution rate and solubility in water, but are sometimes in a slurry state.

In the case of an aqueous solution, the inorganic hydrated ions are bonded to each other or to water molecules and hydrogen bonds, so that a high viscosity solution may be obtained.

The inorganic substance is mixed with water and mixed with isocyanates as an aqueous solution or slurry, but the reaction is initiated by contact with the isocyanates.

The amount of water used when an inorganic substance is used as an aqueous solution or slurry is 50 to 100 parts by weight of the inorganic substance in terms of anhydride. 400 parts by weight is preferred, 100 More preferably 200 parts by weight. If it is less than 50 weight part, workability is bad, and when it exceeds 400 weight part, hardened | cured material of sufficient strength tends to be difficult to be obtained.

Examples of the isocyanates used in the present invention include, but are not particularly limited to, 1) 4-4'-diphenylmethane diisocyanate (MDI), 2,4-triene diisocyanate (TDI), 1,3-xylene diisocyanate ( XDI), hexamethylene diisocyanate (HMDI), polymethylene polyphenyl polyisocyanate (polymeric MDI), and 1,5-naphthalene diisocyanate (NDI), and the like. Modified ③ The terminal isocyanate group containing urethane prepolymer which made these polyisocyanate react with various polyols, (4) The terminal isocyanate group containing urethane prepolymer modified | denatured by water or lower monovalent or polyhydric alcohol, and (5) These terminal isocyanate. Use of one or two or more of the group-containing urethane prepolymers and various polyisocyanates is possible And, again, ① ⑤ One or two or more of them can be used. Among them, the use of polymeric MDI is more preferable in view of stability and economy.

The usage-amount of isocyanates is 80 with respect to 100 weight part of inorganic substances in conversion of anhydride. 1000 parts by weight is preferred, 100 More preferably 600 parts by weight. If it is less than 80 weight part, there exists a tendency for the intensity | strength of hardened | cured material to fall, and when it exceeds 1000 weight part, isocyanate will become excess and there exists a possibility that the intensity | strength of hardened | cured material may fall by unreacted isocyanate.

In general, when the ratio of inorganic to isocyanates increases, the flame retardancy increases but the strength of the cured product decreases. On the contrary, when the ratio of inorganic matter decreases, the flame resistance tends to decrease.

The polyol used in the present invention is to increase the strength of the cured product produced by the reaction between an inorganic substance and an isocyanate, and specifically, polypropylene glycol, polyethylene glycol, trimethylol ethane, trimethylol propane, hexamethylene glycol, And adducts of ethylene oxide or propylene oxide added to alkylene glycol, glycerin, sorbitol or sucrose such as castor oil, ethylene oxide-propylene oxide copolymer and amines such as ethylenediamine, diethanolamine, triethanolamine and triethylenediamine. The adduct which added ethylene oxide and propylene oxide to etc. is mentioned. Among them, the use of adducts in which propylene oxide is added to polypropylene glycol or ethylenediamine is preferable.

The amount of polyol used is 5 per 100 parts by weight of inorganic matter in terms of anhydride. 100 parts by weight is preferable, and in view of strength developability of the cured product obtained, 10 60 parts by weight is preferred. If it is less than 5 weight part, the intensity | strength of hardened | cured material tends to become weak, and when it exceeds 100 weight part, there exists a tendency for flame retardance to fall.

In the case of foaming the cured product produced by the reaction between an inorganic substance and isocyanates, the foam stabilizer used in the present invention stabilizes the foam uniformly, thereby increasing the foaming ratio. If the foam stabilizer is not used in combination, the foam generated by the urethane reaction is broken in turn, and it tends to be obtained only by a cured product having a low foaming ratio. A foaming magnification of 10 times or more can be obtained by using a foam stabilizer, for example, a small amount of silicone foam stabilizer in combination.

Specifically, there are various modified silicone oils such as dimethylpolysiloxane and polyether modified silicone, epoxy modified silicone, amino modified silicone, carboxy modified silicone, methacryl modified silicone, and carbinol modified silicone, and any of them can be used. Although possible, the use of polyether modified silicone oils, such as a dimethylpolysiloxane and / or a dimethylpolysiloxane-polyoxypropylene copolymer which is easy to control bubble size among these, is preferable.

The amount of foam stabilizer is inorganic and 0.01 with respect to 100 parts by weight of water in total. 10 parts by weight is preferred, and 0.05 4 weight part is more preferable. If it is less than 0.01 weight part, foaming ratio will fall, and when it exceeds 10 weight part, there exists a tendency for the balance of foaming and hardening to fall.

The reaction catalyst used in the present invention is a substance having an action of accelerating the isocyanate group reaction to obtain a cured product.

There are various kinds of reaction catalysts, such as an amine catalyst, an organometallic catalyst, and an inorganic catalyst, and each can be used. However, since the activity of the organometallic catalyst is relatively small, the use of an amine catalyst is preferable in terms of environmental conservation.

Examples of the amine catalyst include ethylenediamine, triethylenediamine, triethylamine, ethanolamine, dientanolamine, and hexamethylenediamine or mixtures thereof with derivatives or solvents.

Dibutyltin laurate, dibutyltin diacetate, potassium acetate, etc. are mentioned as an organometallic catalyst.

Tin chloride etc. are mentioned as an inorganic catalyst.

The amount of the reaction catalyst used is not particularly limited, but is 0.1 based on 100 parts by weight of the inorganic substance in terms of anhydride. 10 parts by weight is preferred, and 0.5 5 parts by weight is more preferable. If it is less than 0.1 part by weight, the reaction rate is slow and not practical. If it is more than 10 parts by weight, the reaction rate is too fast, which may inhibit the strength expressability of the cured product obtained.

The solvent used in the present invention is to reduce the viscosity of isocyanates, to adjust the expansion ratio or to improve the reactivity. Specifically, an organic solvent for the purpose of lowering the viscosity, such as toluene, xylene and acetone, methylene chloride Halides, ethers such as tetrahydrofuran, and esters such as methyl cellosolve and acrylic acid ester, and alkylene carbonates such as propylene carbonate.

The usage-amount of a solvent is 5 with respect to 100 weight part of isocyanates. 90 parts by weight is preferred, 10 50 parts by weight is more preferable. If it is less than 5 parts by weight, the viscosity lowering effect is not effective. If it exceeds 90 parts by weight, the viscosity lowering effect is too large, and there is a fear that the mixing properties with the inorganic substance may deteriorate.

Surfactant used by this invention improves the mixing property of inorganic substance, water, and isocyanate, and improves the strength expressability of the hardened | cured material obtained.

Although surfactants include cationic, anionic, nonionic, and cationic surfactants, nonionic surfactants have high reactivity with isocyanates in terms of their structure, and their strength is most preferably expressed.

Examples of the nonionic surfactants include polyoxyethylene alkylphenyl ethers, polyoxyethylene lauryl ethers, and polyoxyethylene octylphenyl ethers.

The usage-amount of surfactant is 5 with respect to 100 weight part of inorganic matter in conversion of anhydride, 40 parts by weight is preferred, 7 20 weight part is more preferable.

If it is less than 5 parts by weight, the isocyanates and water may be separated, and if it exceeds 40 parts by weight, the flame retardancy tends to decrease.

The deodorant used in the present invention refers to a substance which adsorbs or reacts with an odor generated in the curable composition of the present invention and does not generate an odor. Specific examples include ethers, inorganic substances, and water-soluble carboxyl group-containing compounds. Among these, use of a water-soluble carboxyl-group-containing compound is preferred because it is difficult to inhibit the foaming curing reaction.

Here, as a water-soluble carboxyl group-containing compound, there exist a low molecular weight compound and a high molecular compound, either can be used and can also be used together.

As the low molecular weight compound, aromatic carboxylic acids such as acetic acid and propionic acid, aromatic carboxylic acids such as benzoic acid and oxycarboxylic acids such as citric acid, tartaric acid and gluconic acid, or sodium salts and potassium salts thereof can be used.

As a high molecular compound, alginic acid, polyacrylic acid, these sodium salts, potassium salt, etc. can be used.

Among them, the use of oxycarboxylic acid salts and alginic acid salts is preferable from the viewpoint of the control and solubility of the reaction between liquid A and liquid B, and the use of alginic acid salts having a thickening effect and a deodorizing effect is preferable.

Alginate is a polymer of mannuron contained in brown algae, such as kelp and rhubarb, and has a free carboxyl group.

Specifically, alginic acid propylene glycol ester, which is a derivative of alginic acid, and further, various salts such as sodium, potassium and calcium of alginic acid can be used. Of these, the use of sodium alginate salts is preferred, and combinations thereof are also possible.

Alginate raises the viscosity of liquid A to about the same as the viscosity of liquid B. As the viscosity increases, the mixing stability of the liquid A and the liquid B increases, the reproducibility of the reaction becomes good, and furthermore, the presence of the carboxyl group contained in the alginate or the like deodorizes the amine-based odor generated during the reaction. It is also possible.

Although the method of using a deodorant is not specifically limited, Any of the method of mixing in aqueous solution or slurry of an inorganic substance, the method of making into aqueous solution or slurry with an inorganic substance, etc. are possible.

The amount of deodorant used is 0.1 to 100 parts by weight of the inorganic substance in terms of anhydride. 20 parts by weight is preferred, and 0.5 10 weight part is more preferable. If it is less than 0.1 weight part, a deodorizing effect cannot be expected, and when it exceeds 20 weight part, there exists a possibility that it may inhibit foaming hardening reaction.

The flame retardant used in the present invention further improves the flame retardancy of the curable composition, and specific examples thereof include phosphates such as monosodium phosphate, sodium phosphate and sodium tripolyphosphate, colloidal silica, and the like.

The usage-amount of a flame retardant is 1 with respect to 100 weight part of isocyanates. 20 parts by weight is preferred, and 5 10 parts by weight is more preferred. If it is less than 1 part by weight, improvement of flame retardancy cannot be expected, and if it is more than 20 parts by weight, there is a risk of inhibiting the foaming curing reaction.

In this invention, a rise up time modifier can be used as a material which adjusts the hardening time of a curable composition again, and a thickener can be used as a material which increases the viscosity of aqueous solution or slurry of an inorganic substance.

As a rise-up time adjuster, when slowing the hardening time of a curable composition, use, such as monohydric alcohols, such as methanol and ethanol, esters, such as sodium alginate, and inorganic acids, such as hydrochloric acid and a sulfuric acid, is quick, And diamines, such as hexamethylenediamine, and these 1 type, or 2 or more types can also be used together.

The usage-amount of a riseup type adjuster is 0.1 with respect to a total of 100 weight part of inorganic substance and water. 20 parts by weight is preferred, and 0.5 5 parts by weight is more preferable. If it is less than 0.1 weight part, the adjustment effect of hardening time cannot be expected, and when it exceeds 20 weight part, there exists a tendency for reaction to become too fast or too late, and to obtain a favorable hardened | cured material.

Moreover, as a midpoint agent, use of water-soluble polysaccharide is possible. Specifically, methyl cellulose, such as carboxymethyl cellulose or its sodium salt or potassium salt, is mentioned.

Moreover, the water-soluble carboxyl group-containing compound of a deodorant has the gelation effect of the carboxyl group, and can be used also as a midpoint agent.

The usage-amount of a medium-weight agent is 0.1 with respect to 100 weight part of total of inorganic matter and water 5 parts by weight is preferred, and 0.5 2 weight part is more preferable. If the amount is less than 0.1 part by weight, no thickening effect can be expected, and it is difficult to achieve good mixing with the isocyanates under a favorable condition. If it exceeds 5 parts by weight, the viscosity may be excessively increased, making it difficult to adjust the expansion ratio.

The mixing method of the inorganic substance used by this invention, water, isocyanate, and polyol, a foaming agent, a reaction catalyst, a solvent, surfactant, a deodorant, a flame retardant, a rise-up time regulator, and a thickener used together as needed is especially limited. Although not normally, the mixture is stirred well with water and the inorganic substance, the solution A of the aqueous solution or slurry of the inorganic substance is prepared, and the deodorant, the rise-up time adjuster, and / or the thickener are mixed with the polyol, the foam stabilizer and / or the reaction catalyst. It is possible to stir well to make A liquid, and to mix with B liquid of isocyanates.

Moreover, a solvent and surfactant can also be mixed with an inorganic substance, and can also be mixed with an isocyanate.

Although the compounding ratio of A liquid and B liquid is not specifically limited, Usually, A / B is 0.3 It is preferable to mix in the ratio of 2.

The viscosity of the liquid A and the liquid B is not particularly limited, but is usually 400 cpp or less in view of the pumping performance of the pump and the mixing property of the liquid A and the liquid B.

In addition, the feed pressure of the liquid A or liquid B varies depending on the state of the place where the ground is to be injected, and is uniquely difficult. However, when the ground is considerably soft and the ground is likely to collapse, 1 kg / It is preferable to infuse before and after, and 10kg / where there is no collapse of acid It is also possible to inject more than 30 kg / It is preferable to inject below.

Hereinafter, the present invention will be further described based on Examples.

Example 1

To 100 parts by weight of the inorganic material shown in Table 1, water was blended as shown in Table 1 to make A liquid, and 100 parts by weight of A liquid and 100 parts by weight of B liquid made of isocyanates A were mixed. The situation was measured.

The results are shown in Table 1.

(Material used)

Mineral a: Potassium carbonate, Asahi Glass Co., Ltd. industrial use

Mineral b: Sodium aluminate, industrial use made by Showa Denko Co., Ltd.

Inorganic c: Borax (sodium borate), reagent grade 1 manufactured by Kanto Chemical Co., Ltd.

Isocyanates A: Polymeric MDI, commercial item

(How to measure)

Flame retardance: A and B liquids are mixed, and the boric acid index measured after 5 days of mixing is made according to JIS K7201, and a sheet having a thickness of 3 mm is 35 or more. Case was made into x.

Curing condition: When the hardened | cured material obtained after 5 days of mixing of A liquid and B liquid was measured, when it hardened, it was (circle) and it hardened | cured, but when it was weak, (triangle | delta) and the case where it was not hardened, it was set as x.

Water is (parts by weight), flame retardant ○, oxygen index is 28 or more, ○ in the curing state is cured, △ is cured but weak.

Example 2

50 parts by weight of the inorganic material shown in Table 2 and 50 parts by weight of water were mixed in the same manner as in Example 1 except that the polyol and the reaction catalyst α were blended as shown in Table 2 to form A solution. The results are written together in Table 2.

(Material used)

Polyol: Propylene oxide adduct of ethylenediamine, commercial item

Reaction catalyst α: Commercial tertiary amine and main component hexamethylenediamine derivatives.

The polyol and reaction catalyst α is (parts by weight), flame retardant ○ is oxygen index of 28 or more, and ○ in the curing state is cured.

Example 3

50 parts by weight of inorganic a, 50 parts by weight of water, 25 parts by weight of polyol, and α1 part by weight of the reaction catalyst were mixed with a foam stabilizer as shown in Table 3 to make an A solution, and the foaming ratio and curing condition were measured. It carried out similarly to Example 1. The results are written together in Table 3.

(Material used)

Foam stabilizer: For silicone type high elastic foam, Nippon Unicar Co., Ltd. make.

(How to measure)

Foaming magnification: Volume at maximum foaming against the total volume of liquid A and liquid B

The foam stabilizer (part by weight) is cured in the circumstance.

Example 4

50 parts by weight of inorganic a, 50 parts by weight of water, 25 parts by weight of polyol, 1 part by weight of foam stabilizer, and 1 part by weight of reaction catalyst are mixed with surfactant ⓛ as shown in Table 4 to make A solution, and solvent isocyanate A. Was carried out in the same manner as in Example 1, except that Compound B was blended as shown in Table 4 to form B solution. The results are written together in Table 4.

(Material used)

Surfactant ⓛ: Polyoxyethylene nonyl ether, manufactured by Kao Corporation.

Solvent: Propylene carbonate, Showa Denko Co., Ltd.

The surfactant ⓛ and the solvent (parts by weight), flame retardant ○, the oxygen index is 28 or more, and ○ in the curing situation is cured.

Example 5

50 parts by weight of the inorganic substance shown in Table 5, 50 parts by weight of water, 25 parts by weight of polyol, 1 part by weight of foam stabilizer, and 1 part by weight of reaction catalyst α are combined with surfactant ① and deodorant ⓐ as shown in Table 5 It carried out similarly to Example 1 except having used A liquid, the solvent was mix | blended with isocyanate A as shown in Table 5, and it was B liquid, and the smell, flame retardance, and hardening state were measured. The results are written together in Table 5.

(Material used)

Deodorant ⓐ: Sodium alginate, Ganto Kagaku body, reagent grade 1

(How to measure)

Odor: Judgment of odor evaluation was good when ten or more testers smelled and reacted with A deodorant-free A liquid, and when eight or more people felt less smell, it was bad when they felt that there were many smells. .

Surfactant ①, deodorant ⓐ, solvent (parts by weight), good smell, less odor compared to no deodorant, bad smell, more odor, flame retardant ○, oxygen index of 28 or more, hardening ○.

Example 6

50 parts by weight of the inorganic material shown in Table 6, 50 parts by weight of water, 25 parts by weight of polyol, 1 part by weight of foam stabilizer, 1 part by weight of reaction catalyst α, and 1 part by weight of deodorant ⓐ as shown in Table 6 It mix | blended and it was A liquid, and it carried out similarly to Example 1 except having mix | blended flame retardant with isocyanate A as shown in Table 6, and it was B liquid. The results are written together in Table 6.

(Material used)

Flame retardant: Phosphoric acid-based flame retardant.

Surfactant and flame retardant (parts by weight), flame retardant ◎, oxygen index is 35 or more, ○ is 28 or more, ○ in the curing situation is cured.

Example 7

Into 50 parts by weight of inorganic a, 50 parts by weight of water, 25 parts by weight of polyol, and 1 part by weight of reaction catalyst α, a surfactant ① and a midpoint agent are blended as shown in Table 7 to obtain A solution, and the viscosity and curing condition are measured. It carried out similarly to Example 1 except having performed. The results are written together in Table 7.

(Material used)

Emphasis: Alginate Natfume, manufactured by Fujigagaku Co., Ltd.

Surfactant and a medium agent (weight part), ○ of hardening state harden | cure, Experiment number 7-3 has a small amount of water isolate | separates.

Example 8

As shown in Table 8, it carried out similarly to Example 1 except having used A liquid which mix | blended inorganic substance, water, a polyol, reaction catalyst (alpha), and a thickener, and B liquid which consists of isocyanate B shown in Table 8. The results are written together in Table 8.

(Material used)

Isocyanate B: Prepolymer, Mitsui Oatsugagakusa Carbodiimide Modified MDI

Inorganic substances, water, polyols, reaction catalysts α, and a midpoint agent (parts by weight), flame retardant ○, the oxygen index is 28 or more, and ○ in the curing state is cured.

Example 9

Change the type and amount of the inorganic substance as shown in Table 9, and mix water, polyol, foam stabilizer, reaction catalyst α, and surfactant ① with 1 part by weight of the inorganic substance and deodorant ⓐ as shown in Table 9 It carried out similarly to Example 1 except having used as a liquid and mix | blending a solvent with isocyanates as shown in Table 9 to make B liquid. The results are written together in Table 9.

(Material used)

Mineral d: Sodium carbonate, reagent grade 1 manufactured by Kanto Chemical Co., Ltd.

Mineral e: Sodium sulfate, reagent grade 1 manufactured by Kanto Chemical Co., Ltd.

Inorganic substances, water, polyols, foam stabilizers, reaction catalysts α, surfactants ① and solvents (parts by weight), flame retardant ○, the oxygen index is 28 or more,-is not measurable, ○ in the curing conditions, ○ is cured, △ is cured But weak.

Example 10

100 parts by weight of the inorganic material shown in Table 10 and 2 parts by weight of the reaction catalyst? The results are written together in Table 10.

(Material used)

Inorganic f: lithium carbonate, reagent grade 1 made by Kanto Chemical Co., Ltd.

Inorganic g: aluminum oxide, reagent grade 1 manufactured by Kanto Chemical Co., Ltd.

Mineral h: Sodium nitrate, reagent grade 1 manufactured by Kanto Chemical Co., Ltd.

Mineral i: Sodium tripolyphosphate, reagent grade 1 manufactured by Kanto Chemical Co., Ltd.

Mineral j: Sodium hydroxide, reagent grade 1 manufactured by Kanto Chemical Co., Ltd.

Inorganic k: potassium carbonate / sodium aluminate = 50/50 weight ratio mixture

Polyol (parts by weight), flame retardant ○ is oxygen index of 28 or more, and

Example 11

100 parts by weight of the inorganic material shown in Table 11, 4 parts by weight of the reaction catalyst α, and 10 parts by weight of the surfactant ② are mixed with water as shown in Table 11 to form A solution, and isocyanate to 100 parts by weight of A solution. 100 parts by weight of liquid B, a liquid, was blended, and the curing time, foaming ratio, compressive strength, oxygen branch, and flame resistance were measured. The results are written together in Table 11.

(Material used)

Surfactant ②: Daiichi Kogyo Seiya Corporation, main component polyethylene alkyl phenyl ether

(How to measure)

Cure time: Time until the maximum foaming time after mixing A liquid and B liquid.

Compressive strength: A mixture of liquid A and liquid B was placed in a formwork having a length of 2 cm x 2 cm x 2 cm, and the strength was measured 24 hours after molding.

Oxygen index: 3 mm thick sheet was prepared and measured in accordance with JIS K 7201.

Water is in parts by weight, curing time in seconds, and compressive strength is in kgf / ), Flame retardant ○ is oxygen index of 28 or more.

Example 12

Ten 3m injection bolts were inserted in a 1m pitch at a 25 degree angle into the ceiling of a tunnel site with many unstable rocks with many cracks.

With a gear pump capable of equally conveying the amount of the inorganic a, 100 parts by weight of water, 100 parts by weight of water, 4 parts by weight of the reaction catalyst α, and 10 parts by weight of the surfactant ② and the liquid B of the isocyanates B, each minute 2 Pressure 10kg / Through a static mixer installed at the inlet of the bolt, and mix A and B liquids at 30 per bolt. , 300 total Injected.

As a result of excavation 1 hour after the injection, there was no collapse of the ceiling, and the effect of injecting the chemical liquid of the present invention was sufficiently confirmed.

Example 13

It carried out similarly to Example 12 except having used A liquid which consists of 100 weight part of inorganic a, 100 weight part of water, 4 weight part of reaction catalysts (alpha), and 10 weight part of surfactant (2).

As a result of excavation 1 hour after the injection, there was no collapse of the ceiling, and the injection effect of the chemical liquid of the present invention was sufficiently confirmed.

Example 14

100 parts by weight of the inorganic material shown in Table 12, 100 parts by weight of water, 100 parts by weight of water, and 4 parts by weight of the reaction catalyst? It carried out similarly to Example 11. The results are written together in Table 12.

(Material used)

Surfactant (3): Polypropylene-type polyol, the Mitsui Otsu Chemical Co., Ltd. make.

Surfactant ④: Castor oil-based polyol. Ito Oil Company

Surfactant (parts by weight), curing time (seconds), compressive strength (kgf / ), The flame retardant ○ is not measured because the oxygen index and flame retardancy of the oxygen index 28 or more, Experiment Nos. 12-1, 12-2 and 12-12.

Example 15

100 parts by weight of the inorganic material shown in Table 13, 100 parts by weight of water, and 4 parts by weight of the reaction catalyst α are mixed with 10 parts by weight of the type of surfactant as shown in Table 13 to obtain A solution, curing time, foaming ratio, And it carried out similarly to Example 11 except having measured the compressive strength. The results are written together in Table 13.

(Material used)

Surfactant (5): Gao Corporation make, polycarboxylic acid type polymeric surfactant.

Surfactant ⑥: Gao Corporation, lauryl trimethylammonium chloride type

Surfactant (parts by weight), curing time (seconds), compressive strength (kgf / ).

Example 16

Inorganic a 100 parts by weight, reaction catalyst α 1 part by weight, surfactant ③ 10 parts by weight, 100 parts by weight, a deodorant is blended as shown in Table 14 to the liquid A, isocyanate liquid with respect to 100 parts by weight of liquid A 100 parts by weight of liquid B, which is A, was mixed, and its rise time, foaming ratio, compressive strength, oxygen index, flame retardancy, and smell were measured. The results are written together in Table 14.

(Material used)

Deodorant ⓑ: 1st grade reagent made by Alginic acid, Wakojun Yakugo teacher

Deodorant ⓒ: Alginate Sodium / Alginate Weight Ratio 1

Deodorant ⓓ: Sodium citrate, Wakojun Yakugo teacher's reagent grade 1

(How to measure)

Rise Up Time: The time until the A solution and the B solution are mixed, reacted and foamed to swell and stop.

Deodorant (parts by weight), rise up time (seconds), compressive strength (kgf / ), Flame retardant ○ has an oxygen index of 28 or more, and the smell is less than the deodorant additive.

Example 17

It carried out similarly to Example 16 except having used the inorganic substance e as an inorganic substance. The results are shown in Table 15.

Deodorant (parts by weight), rise up time (seconds), compressive strength (kgf / ), Flame retardant ○ has an oxygen index of 28 or more, and the smell is less than the deodorant additive.

Example 18

Example 16 except that 100 parts by weight of the inorganic material shown in Table 16, 1 part by weight of the reaction catalyst α, 10 parts by weight of the surfactant 3 and 2 parts by weight of the deodorant ⓐ were mixed with water as shown in Table 16 to make A solution. The same was done.

The results are written together in Table 16.

Water (parts by weight), Rise-up time (seconds), Compressive strength (kgf / ), Flame retardant ○ is oxygen index 28 or higher, the smell is less odor compared to the deodorant-free.

Example 19

100 parts by weight of the inorganic material shown in Table 17, 100 parts by weight of water, 10 parts by weight of the surfactant ③, and 2 parts by weight of the deodorant ⓐ in the form of A liquid by changing the type and amount of the reaction catalyst as shown in Table 17. Other things were the same as in Example 16. The results are written together in Table 17.

(Material used)

Reaction catalyst β: commercial tertiary amine, main component dimethylamine derivative

Reaction catalyst (parts by weight), rise up time (seconds), compressive strength (kgf / ), Flame retardant ○ is more than oxygen index 28, odor is less odor compared with no deodorant,-is not measured due to poor curing.

Example 20

100 parts by weight of inorganic matters shown in Table 18, 100 parts by weight of water, 1 part by weight of reaction catalyst α, and 2 parts by weight of deodorant ⓐ, except that the type and amount of the surfactants were changed as shown in Table 18 to prepare a solution A. It carried out similarly to Example 16. The results are written together in Table 18.

Surfactant (parts by weight), rise up time (seconds), compressive strength (kgf / ) Flame retardant ○ is more than oxygen index of 287, the smell is less than the smell of deodorant. -Cannot be measured due to lack of strength

Example 21

100 parts by weight of the inorganic a, 100 parts by weight of water, 1 part by weight of the reaction catalyst α, 10 parts by weight of the surfactant, and 2 deodorants of the deodorant ⓐ 2 are combined to make A solution. Similarly, it carried out similarly to Example 16 except having mix | blended B liquid which changed the kind and quantity of isocyanate. The results are written together in Table 19.

Liquid B (parts by weight), Rise-up time (seconds), Compressive strength (Kgf / ), Flame retardant ○ Good oxygen index of 28 or more, the smell is less than the smell of deodorant.

Example 22

Into the ceiling of a tunnel site with many unstable rocks with cracks, 10 injection bolts of 3 m were inserted at 1 m pitch at an angle of 25 degrees.

100 parts by weight of inorganic a, 100 parts by weight of water, 1 part by weight of reaction catalyst α, 10 parts by weight of surfactant ③, and 2 parts by weight of deodorant ⓐ are mixed to adjust liquid A, and the liquid B is adjusted using isocyanate A. did.

It is 2 every minute with gear pump which can equally pump this A liquid and B liquid Pressure 10 Kgf / And mix A and B liquids through a static mixer installed at the inlet of the bolts. , 300 total Injected. As a result of excavation 1 hour after the injection, there was no collapse of the ceiling and the injection effect of the present invention was sufficiently confirmed.

Example 23

It carried out similarly to Example 22 except having mix | blended A liquid by mixing 100 weight part of inorganic materials e.

As a result of excavation after 1 hour of injection, there was no collapse of the ceiling, and the effect of injection of the chemical liquid of the present invention was sufficiently confirmed.

Example 24

Three injection bolts with a length of 1 m were inserted into a gap of about 1.5 ㎥ formed between Jishan and perforated concrete.

100 parts by weight of the inorganic a, 100 parts by weight of water, 1 part by weight of the reaction catalyst α, 40 parts by weight of the surfactant ③, and 1 part by weight of the deodorant ⓐ were mixed to make the A liquid, and the isocyanate A was used as the B liquid.

3 kg / with gear pump that can equally pump this liquid A and liquid B 5 minutes at a pressure of 100 per one injection bolt while mixing A and B liquids through a static mixer installed at the inlet of the injection bolt. 300 total Injected.

One hour after the injection, a core having a diameter of 5 cm was taken and observed, and the foamed cured product was sufficiently filled between the acid and the perforated concrete, and the injection effect of the present invention was confirmed.

By using the inorganic substance and isocyanate of the curable composition of this invention, organic-inorganic composite was formed and a flame-retardant foam hardened | cured material was obtained.

In addition, the amine odor generated during the reaction can be considerably reduced, and an excellent material considering sufficient stability and workability can be obtained.

Moreover, by using a rise-up time adjuster, hardening rate can be adjusted and adjustment in the present situation becomes easy.

Moreover, adjustment of foaming ratio became easy by using a foam stabilizer.

And by using a thickener, the mixing property with isocyanates can be improved.

Moreover, since this invention product is comprised from inexpensive material compared with the polyol which is a component of A liquid conventionally used, it is a low cost material.

Moreover, by using the curable composition of this invention, the effect of being able to fully inject | pour into a soft ground, a cavity of a rock, and a space, such as a acid and perforated concrete, is exhibited.

Claims (6)

Inorganic compounds selected from potassium carbonate, sodium aluminate, sodium borate, sodium carbonate, sodium sulfate, sodium nitrate, sodium tripolyphosphate, sodium hydroxide, potassium carbonate / sodium aluminate = 50/50 weight ratio mixture, lithium carbonate, and aluminum oxide And water and isocyanate, containing polymethylenepolyphenylpoisocyanate (polymeric MDI), wherein water is 50-400 parts by weight based on 100 parts by weight of inorganic matter in terms of anhydride, and isocyanate is 80- parts by weight of 100 parts by weight of mineral in terms of anhydride. 1000 parts by weight, and further includes an alkylene carbonate solvent, a nonionic surfactant, or a mixture thereof, based on 100 parts by weight of isocyanate, 5-90 parts by weight of solvent, and 100 parts by weight of inorganic agent 5- Curable composition containing 40 weight part. The method of claim 1, further comprising an additive selected from polyol, a silicon foam stabilizer, and a tertiary amine catalyst, which are propylene oxide adducts of ethylenediamine, wherein the polyol is 5-100 parts by weight based on 100 parts by weight of an inorganic substance of anhydride volcano, A foam stabilizer is 0.01-10 parts by weight relative to a total of 100 parts by weight of an inorganic substance and water, and a catalyst is contained in 0.1-10 parts by weight based on 100 parts by weight of an inorganic substance in terms of anhydride. The composition according to claim 1 or 2, further comprising a deodorant, which is contained in an amount of 0.1-20 parts by weight based on 100 parts by weight of the inorganic substance in terms of anhydride. The composition of claim 3, further comprising a flame retardant, wherein the flame retardant is contained in an amount of 1-20 parts by weight based on 100 parts by weight of isocyanate. The ground stabilization method characterized by injecting the curable composition according to claim 1 or 2. A ground solution stabilizing method comprising mixing and injecting an A solution containing an aqueous solution or slurry of the inorganic compound according to claim 1 and a B solution containing an isocyanate at an A / B blending ratio of 0.3-2.