JPH108051A - Solidification grout for soil improvement and impregnation and consolidation using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject grout useful for improving the qualities of soil of poor ground, capable of enriching elasticity and exhibiting long-term persist ence, by using a hydraulic prepolymer composition comprising specific components. SOLUTION: This grout comprises (A) 100 pts.wt. of an active silyl group- containing prepolymer which contains at least >=1.2 active silyl group ends of the formula (R<1> is Cl, H methyl, ethyl or propyl; X is a 1-5C alkoxyl, oxime or acetoxyl; (n) is 0 or 1) in one molecule on the average shows siloxane cross- linking properties by hydrolysis, has <=20 deg.C glass transition temperature of an organic polymer chain part of the main chain except the silyl group and 500-20,000 weight-average molecular weight, (B) 10-200 pts.wt. of a flame- retardant phosphoric acid alkyl ester-based plasticizer and (C) 0.1-20 pts.wt. of an organic acid derived from a natural substance. Preferably, the component B is tris-β-chloropropyl phosphate and the component C is phytic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an injection consolidation agent for ground improvement (hereinafter sometimes referred to as a grouting agent) and a ground injection consolidation method using the same (hereinafter sometimes referred to as a grouting method). . Specifically, one shot injection method ~
The present invention relates to a permanent and elastic organic polymer-based injection consolidation agent for soil improvement, which can be handled by any of the two-shot injection methods, and a method of manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, various grouting agents have been used as a grouting agent for improving and stabilizing the ground. The most frequently used ones at present include water-glass or cement-based inorganic grouting agents. Various polymer grouting agents have been developed from the late 1960s to 1990, and for example, acrylamide grouting agents, urea grouting agents, urethane grouting agents, and the like have been proposed.

On the other hand, as a prior art relating to a permanent or durable grouting agent, for example, Japanese Patent Application Laid-Open No. Sho 59-4 is disclosed.
No. 9283 discloses a water glass grouting agent using slag and lime.
No. 5 discloses a highly durable grout comprising water glass, slag, cement, and lime. In recent years, Japanese Patent Application Laid-Open No. 6-41533 discloses a non-aqueous glass suspension comprising granulated slag made of high-purity glass having a calcium oxide content of 20 to 50% by weight and an alkaline solution such as sodium hydroxide. There has been proposed a turbid slag type high strength type grouting agent. Thus, in recent years, durability and high-strength functions have been strongly demanded. Among them, expectations for organic polymer grouting agents, which are generally considered to be rich in chemical resistance, have increased in recent years.

[0004] Among the conventional organic polymer grouting agents,
Acrylic amide grouting agents and the like are currently prohibited from domestic use because uncured monomers penetrate into groundwater, causing water pollution and causing pollution problems. In addition, urea grouting agents generally have an inherent problem of storage stability, and it is said that they still have a problem in construction management in summer.

[0005] Urethane grouting agents are disclosed in, for example, JP-A-48-15315 and JP-A-48-6970.
No. 1 proposes for the first time that the compact is said to realize particularly high strength. Also, Japanese Patent Application Laid-Open No. 55-65212
In the publication, a water glass-urethane grout agent is disclosed, and it has been proposed to have an advantage that the impregnating property and the consolidation volume can be increased by foaming and consolidating urethane. A track record has been achieved. However, general urethane grouting agents often have a problem that foaming is rapid and handling and adjustment of injection pressure are complicated. In addition, to handle a large amount of isocyanate compounds harmful to the human body,
It is a grouting agent that can be injected into the ground only when a limited and emergency response is required.

As described above, the conventional organic polymer grouting agent does not always satisfy the requirements in the art. Therefore, the main grouting agent that can be selected when injecting into the ground where it is desired to ensure durability is mainly a suspension type inorganic grouting agent such as fine particle cement, etc., and a permanent soil strengthening method is implemented by a jet grouting method etc. That is the reality. However, it is known that it is difficult to employ the cement-based grouting agent by the infiltration and consolidation method. In order to secure sufficient permeability, it is essential to make cement particles into ultra-fine particles having a maximum size of 10 μm or less. There is a problem that such ultra-fine cement cannot be produced in a very small amount in Japan at present, so that there is no stability in mass supply.

Further, in recent years, the appearance of a high-strength and permanent grout agent exceeding the solidified strength of a water-glass grout agent has been desired for the following reasons. The damage of the Great Hanshin Earthquake that occurred in January 1995 was caused by a great deal of damage to structures built on soft ground and underground.
It can be said that this has raised major issues such as the method of restoration, ensuring the safety of all structures on unstable ground, and the method of permanent reinforcement against earthquakes. In particular, there is a strong demand for ensuring the safety of various publicly important structures already constructed on the ground where liquefaction is expected in major urban areas.
There is a strong need to provide a new, reliable, permanent grouting agent early on the market. Also,
It is indispensable to secure and reinforce the ground in order to construct a new large structure on or in soft ground such as a landfill or sandy ground.

[0008] Under these circumstances, expectations for a new organic polymer grouting agent generally considered to be rich in chemical resistance have been increased in recent years. Many low-viscosity organic polymer grouting agents can be handled in solution, and if they can simultaneously exhibit high permeability and various functions, they are expected to be permanent grouting agents, but they have excellent flexibility and rigidity. As described above, no high-quality grouting agent having very low toxicity has been found.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an organic polymer grouting agent capable of constructing a soil with high durability and durability. Another object of the present invention is mainly composed of a liquid component, and can easily adjust the gel time in an arbitrary range such as high permeability, instantaneous setting (several seconds of gelation) to long setting (several hours of gelation), Further, it is an object of the present invention to provide an organic polymer grouting agent having properties such as a final injection-molded compact (homogel and sandgel) which is rich in toughness and can ensure high compressive strength stability for a long period of time.

Still another object of the present invention is to easily handle any one-shot system or two-shot system,
An object of the present invention is to provide an organic polymer grouting agent that can easily perform injection control, is flame-retardant, and ensures safety at an injection work site. Still another object of the present invention is to provide a highly safe organic polymer grouting agent which has a property of being basically solidified by contact with moisture, and in which groundwater elution and contamination of the main component is significantly reduced. That is. Still another object of the present invention is to provide an organic polymer grouting agent that has extremely low water permeability of the injected solidified body and can be expected to have a water stopping effect.

[0011]

Means for Solving the Problems As a result of intensive studies, the present inventor has solved the above-mentioned object by using a water-curable prepolymer-containing composition comprising specified components as a grout injection chemical solution. And found that the present invention was achieved. That is, the present invention relates to a compound represented by the formula (1) showing a property of crosslinking with siloxane by hydrolysis.

[0012]

Embedded image-(CH ₂ ) ₃ -Si (R ¹ ) _n- (X) _3-n (1) (where R ¹ is a chlorine atom, a hydrogen atom, a methyl group, an ethyl group or a propyl group, and X is Represents an alkoxyl group, an oxime group, or an acetoxyl group having 1 to 5 carbon atoms, and n is 0 or 1.) The glass transition temperature of the organic polymer chain long part of the main chain excluding the active silyl group is 2
0 ° C. or lower and weight average molecular weight of 500 to 20,000
Active silyl group-containing prepolymer (a) 10
Permanent, comprising 10 to 200 parts by weight of a flame-retardant alkyl phosphate plasticizer (b) and 0.1 to 20 parts by weight of an organic acid derived from a natural product (c) per 0 parts by weight. It is an elastic organic polymer-based injection consolidation agent (grout agent) for ground improvement.

Preferably, the active silyl group-containing prepolymer is such that R ^{1 in} the formula (1) is a methyl group or an ethyl group, X is an alkoxyl group having 1 to 5 carbon atoms, and the terminal of the active silyl group is in one molecule. The glass transition temperature of the organic polymer chain long part of the main chain excluding the active silyl group is at least 2 ° C. and the weight average molecular weight is 1,000 to 5,
000, wherein 100 to 100 parts by weight of the active silyl group-containing prepolymer contains 30 to 100 parts by weight of a flame-retardant alkyl phosphate plasticizer and 1 to 10 parts of a natural product-derived organic acid. The injection consolidation agent for soil improvement described above is a part by weight.

Further, the present invention relates to a method for stabilizing soft ground, wherein one of a one-shot method, a 1.5-shot method and a two-shot method is provided through an injection pipe buried in the ground. The above-mentioned organic polymer grouting agent is injected while being pressurized, and a ground injection consolidation method for consolidating and stabilizing the ground, through an injection pipe buried in the ground, first of the organic acid derived from natural products After the dilute solution is injected, the grouting agent is injected while pressurizing the ground injection consolidation method, and is provided at a constant interval to an unstable portion at the boundary between the underground concrete and the ground. A ground injection consolidation method characterized by injecting the above grouting agent under pressure through a hollow anchor bolt material also serving as an injection conduit.

Several organic polymer precursors exhibiting the property of gelling and crosslinking upon contact with moisture have been known. Known representative precursors include those having an isocyanate group and those having a hydrolytically active silyl group introduced at the terminal.In the field of grout injection medicine,
Only those having the former isocyanate group are known. The latter is known, for example, in Japanese Patent Publication No. 61-18852, but most of it is limited to the adhesive field, the coating field, and the sealant field, and is used to stabilize the injection consolidation of soft ground. There is no disclosure of a composition suitable for the so-called grouting agent for ground injection, which is an agent, or a method of solidifying the ground injection.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In summary, the grouting agent of the present invention comprises, as essential components, three components of an active silyl group-containing prepolymer (a), a flame-retardant alkyl phosphate plasticizer (b), and an organic acid derived from a natural product (c). I do.

The active silyl group-containing prepolymer (a) is
An active silyl group-modified resin which is liquid at room temperature and has a rubbery shape at room temperature, and can be obtained by a known method, and there is no particular limitation on the production method. In the above formula (1) in the prepolymer (a), X is preferably a methoxy group or an ethoxy group, and particularly preferably an ethoxy group. The prepolymer (a) has at least 1.2 or more active silyl group terminals in one molecule on average. If the number is less than 1.2, it will not be a ground improvement injection agent exhibiting sufficient compressive strength. Preferably, the number is 2 to 6 on average.

The weight average molecular weight of the main chain organic polymer is 500
~ 20,000. If it is less than 500, the toughness of the grout agent is slightly inferior. If it exceeds 20,000, the rigidity is insufficient and the viscosity of the agent is too high, so that sufficient ground permeability cannot be secured. In particular, the weight average molecular weight of the main chain organic polymer is 1,000.
When it is 5,000, the prepolymer (a) can be made into a relatively low-viscosity body, which is preferable. The glass transition temperature of the organic polymer chain long part of the main chain excluding the active silyl group of the prepolymer (a) is 20 ° C. or less. If the temperature exceeds 20 ° C., the toughness of the grout agent becomes insufficient. Preferably -100 ° C below 0 ° C
That is all.

The prepolymer (a) specifically has a so-called polyether polymer chain length having a main skeleton of, for example, a polyether polyol derived from a polyalkylene oxide and is represented by the above formula (1). Terminal silyl group-modified polyether prepolymer, polybutadiene polymer chain length having polybutadiene polymer chain length represented by the above formula (1), hydrogenated derivative thereof, polyisoprene polymer chain length A polyisoprene-based prepolymer modified with a terminal silyl group represented by the formula (1) and a hydrogenated derivative thereof, and a polydimethylsiloxane polymer having a chain length and a terminal silyl group represented by the formula (1) Modified silicone oil-based prepolymer, polyetherester having a polymer chain length of the general formula (1)
A polyester liquid prepolymer modified with a terminal silyl group, a polycarbonate prepolymer modified with an aliphatic polycarbonate polymer having a polymer chain length and represented by the above formula (1), an alkyl (meth) acrylate And an acrylic rubber-based prepolymer modified with a silyl terminal group represented by the above formula (1) and having a polymer chain length of a liquid acrylic rubber induced by polymerization of the same. Among these prepolymer types, polyether-based prepolymers are preferable in terms of economy.

As a method for producing the prepolymer (A), for example, a method for producing a silyl-modified composition having a polyether skeleton represented by JP-A-50-156599 or JP-A-53-139699 The method for producing a silyl-modified composition having a polyester skeleton represented by the formula (1) can be specifically applied.

Further, in the present invention, a prepolymerized precursor material can be easily obtained on the market, a prepolymer can be produced by a one-step reaction, and a prepolymer having low toxicity and excellent storage stability can be derived. Since the presence of urethane bonds in the molecular chain can be expected to improve the reliability of adhesion to the clay and sand components that constitute the ground, a preferred prepolymer (a) is a prepolymer solution containing an active silyl group.
The total weight average hydroxyl value is 10 to 450 mg KOH
/ G of a polyol, preferably a polyol which is liquid at normal temperature, and the following formula (2)

[0022]

Embedded image OCN—R ² —Si (R ¹ ) _n — (X) _3-n (2) (wherein R ² has 3 or more carbon atoms, preferably 3 to 6 carbon atoms)
R ¹ represents a methyl group, an ethyl group or a propyl group, X represents an alkoxyl group having 1 to 5 carbon atoms, and n represents 0 or 1. And the isocyanate silane represented by the formula (1) in the range of 0.5 to 3.0 in NCO / OH equivalent ratio.

Most preferably, the total weight average hydroxyl value of the polyol is from 25 to 300 mg KOH.
Diol or triol that is liquid at room temperature in the range of / g and has an NCO / OH equivalent ratio in the range of 0.95 to 1.05. Hereinafter, the prepolymer (a) derived from the polyol and the isocyanate silane of the above formula (2) may be particularly referred to as a G prepolymer.

In the present invention, the above-mentioned polyol is preferably liquid at room temperature. However, the term "liquid at room temperature" refers to the case where the polyol is used alone at room temperature or when two or more polyols are used in combination. Even if at least one of them is solid at room temperature, it is included if the mixture is liquid at room temperature. In particular, a polyol component which is solid at room temperature is contained in all polyols.
Those which are used together within 5% by weight and which maintain the liquid at normal temperature can be preferably used. Furthermore, the prepolymer (a) finally derived by mixing well with the flame-retardant alkyl phosphate ester plasticizer (b), which is an essential component, and the organic acid (c) derived from natural products, A polyol that can stably maintain a liquid or micro suspension at room temperature can be selected and used.

However, when the polyol has a high crystallinity in the polymer chain length, the derived final reaction product easily retains the property of a bulk solid at room temperature. Unsuitable as a grouting agent. A highly crystalline polyol is unlikely to be a grouting agent having toughness and flexibility, and a known crystalline polyol having a melting point of 60 ° C. or more and being solid at room temperature is not preferred. The total weight average hydroxyl value described above represents the average hydroxyl value of all polyol components when the same or different polyol components having different molecular weights are used alone and / or in combination.

The polyol which is a starting material for synthesizing the G prepolymer has a total weight average hydroxyl value of 10%.
４５０450 mgKOH / g, and within this range, the flexibility of the obtained grout agent and the uniaxial compressive strength and rigidity are ensured in a well-balanced manner. Hydroxyl value is 10mgKO
When a polyol having an H / g content of less than H / g is used, the resulting G prepolymer tends to be a high-viscosity composition, lacks storage stability, and has a low homogel strength due to insufficient crosslink density of the final grout solidified product. The hydroxyl value is 450m
When a polyol exceeding gKOH / g is used, the production cost of the derived G prepolymer tends to be high, and the final grout consolidated product is hard and brittle.

Known polyols may be used and are not particularly limited, and specific examples thereof include the following (a) to (h). (A) Polyether polyol (b) Telechelic acrylic polyol (c) Polyisoprene diol and / or hydrogenated product thereof (d) Polybutadiene diol and / or hydrogenated product thereof (e) Silicon polyol (f) Polycarbonate polyol (g) ) Amorphous polyester polyol (h) Amorphous polyether polyester polyol

The polyether polyol (a) may be a known one, and there are no particular restrictions on the production method and the like. For example, water, trimethylolpropane, glycerin, neopentyl glycol, sucrose, triethanolamine, ethylenediamine Inexpensive active hydrogen compounds such as ethylene oxide (EO) and propylene oxide (P
O), butylene oxide (BO), tetrahydrofuran and the like, and a material obtained by reacting them by a method such as anionic polymerization or cationic polymerization are preferred examples. A diol having two hydroxyl groups in one molecule and a triol having three hydroxyl groups in one molecule can be particularly preferably used.

Of the above-mentioned alkylene oxides, E
The molar ratio of addition polymerization of O and PO is (50: 5
2) having a terminal primary and / or secondary OH group obtained by acting in the range of 0) to (0: 100).
Functional polyols are more preferred. The polyol represented by (a) is relatively inexpensive, easily available on the market, and can easily prepare a low-viscosity G prepolymer solution. (A) is a weight average molecular weight expressed in terms of polystyrene determined by liquid chromatography or a weight average molecular weight calculated from a hydroxy value of 500 to 20,
It is important to set the range to 000, preferably 1,000 to 5,000.

(B) Telechelic acrylic polyol means an acrylic polyol which is liquid at room temperature and has a hydroxyl group selectively introduced at a molecular terminal. Examples of the synthesis and production methods are already disclosed in JP-A-4-132706 and JP-A-5-262808, and may be obtained by a known method, and there is no particular limitation. The general (b) includes those in which two hydroxyl groups are introduced on average in one molecule. (B) is a weight-average molecular weight expressed in terms of polystyrene determined by liquid chromatography or a weight-average molecular weight calculated from a hydroxy value in the range of 500 to 20,000, preferably 1,000 to 5, It is important to set the range to 000.

(C) polyisoprene polyol and / or
Alternatively, the hydrogenated product is a compound obtained by using isoprene as a main starting material and having at least 1.2 hydroxyl groups, preferably 2 to 2 hydroxyl groups in one molecule obtained using a known polymerization initiator.
About 6 polyisoprenes and / or hydrogenated products thereof can be preferably used. The production method and the like of (c) are not particularly limited, and known methods and commercially available products can be used.
(C) is a weight average molecular weight expressed in terms of polystyrene determined by liquid chromatography or a weight average molecular weight calculated from a hydroxy value of 500 to 20,000.
It is important to set the range to 0, preferably 1,000 to 5,000.

(D) polybutadiene polyol and / or
Alternatively, the hydrogenated product thereof includes butadiene as a main starting material, and has at least 1.2 or more, preferably 2 to 2, hydroxyl groups in one molecule obtained using a known polymerization initiator.
About 6 polybutadienes and / or hydrogenated products thereof can be preferably used. The production method and the like of (d) are not particularly limited, and a product obtained by a known method or a commercially available product can be used. (D) is a weight-average molecular weight expressed in terms of polystyrene determined by liquid chromatography or a weight-average molecular weight calculated from a hydroxy value of 500 to 2;
In the range of 0,000, preferably 1,000-5,000
It is important to set the range as follows.

(E) Silicone polyols are those having a repeating chain length of dimethylsiloxane units or methylphenylsiloxane units and having a hydroxyl group introduced directly at the molecular terminal of the chain polymer or a polyether-based compound at the molecular terminal. And a product obtained by a known method or a commercially available product can be used.
At least 1.2 hydroxyl groups are present on average in one molecule of (e), and although there is no particular limitation, about 2 to 6 hydroxyl groups can be preferably used. (E) is a weight average molecular weight expressed in terms of polystyrene determined by a liquid chromatography method or a weight average molecular weight calculated from a hydroxy value in the range of 500 to 20,000, preferably 1,000 to 5, It is important to set the range to 000. More specifically, dimethyl polysiloxane diol, methyl phenyl polysiloxane diol, dimethyl polysiloxane dipropylene glycol, dimethyl polysiloxane dipropylene ethylene glycol, dimethyl polysiloxane diethylene glycol, methyl phenyl polysiloxane dipropylene glycol, methyl phenyl polysiloxane diethylene glycol, etc. Is raised.

(F) The polycarbonate polyol is
A compound containing a lactone ring as a main starting material,
A ring-opening polymerization reaction was carried out in the presence of a known ring-opening catalyst, and the weight-average molecular weight was 500 to 20, which was calculated from a polystyrene-equivalent value or a hydroxy value, which was determined by liquid chromatography. 000, preferably 1,000 to 5,000. There is no particular limitation on the production method and the like, for example, polyethylene carbonate diol, polypropylene carbonate diol, polybutylene carbonate diol, etc., which can be easily obtained on the market.

(G) The amorphous polyester polyol is a semi-solid or liquid at room temperature, and is a weight calculated from a weight average molecular weight or a hydroxy value expressed in terms of polystyrene determined by a liquid chromatography measurement method. It is a so-called polyester having a terminal hydroxy group having an average molecular weight in the range of 500 to 20,000, preferably 1,000 to 5,000. The (g) is
It had about 2 to 4 hydroxyl groups as a hydroxyl group in one molecule,
So-called known flexible polyesters are mentioned as preferred examples. Although not particularly limited, specific examples of (g) include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, propylene carbonate diol, A product obtained by subjecting at least one kind of ethylene carbonate diol, trimethylolpropane, silicon polyol, acrylic polyol, hydrogenated olefin polyol, and the like to a known organic dibasic acid to an esterification reaction, and a melting point or a penetration method Any rubbery semisolid having a Tg of 20 ° C. or less or a liquid at room temperature can be used.

(H) Amorphous polyether polyester polyol is a semi-solid or liquid at room temperature and a weight calculated from a weight average molecular weight or a hydroxy value expressed in terms of polystyrene determined by a liquid chromatography measurement method. It is a so-called soft polyether polyester having an average molecular weight in the range of 500 to 20,000, preferably 1,000 to 5,000. (H) is a cyclic compound having at least 1.2 or more, preferably 2 to 4 hydroxyl groups as a terminal functional group in one molecule and having a polyether chain having a degree of polymerization of 10 or more and 50 or less. A preferred example is a soft polyether polyester having units. Although not particularly limited, for example, a molecular weight of 5
A polyether polyol of about 00 to 1000 and a known organic dibasic acid are subjected to an esterification reaction, and a rubbery semisolid having a melting point or Tg of 20 ° C. or less measured by a penetration method or a room temperature. And liquid is typical.

Among these, in the G prepolymer, the value of the total average hydroxyl value of the polyol is more preferably in the range of 20 to 350 mgKOH / g, more preferably in the range of 25 to 300 mgKOH / g and normal temperature. The liquid polyols (a) to (e) are preferred,
It is preferable to use at least one kind or two or more kinds selected from these, and particularly preferable polyols are polyether diols and / or triols. The above-mentioned at least one polyol (a) to (h), more preferably (a) to (e), and the isocyanate silane represented by the formula (2) are hydrolyzed to the molecular terminal of the present invention. A G prepolymer having a reactive silyl group (also called an active silyl group) is easily formed.

The isocyanate silane represented by the formula (2) is not particularly limited, but specifically, for example, γ-isocyanatopropyltriethoxysilane,
γ-isocyanatopropyltrimethoxysilane, γ-
Isocyanatopropyldiethoxymethylsilane, γ-
Isocyanatopropyldimethoxymethylsilane and the like are known, and one or more selected from them may be selected and used.

The G prepolymer having an active silyl group at the molecular terminal of the present invention is preferably the aforementioned (a) to (a).
(E) any one of the polyols and the above-mentioned isocyanate silane in an NCO / OH equivalent ratio of 0.5 to 3.0;
If necessary, a known urethanization catalyst may be used at an equivalence ratio as close as possible, preferably in the range of 0.9 to 2.0, particularly preferably in the range of 0.95 to 1.05, and most preferably in the range of 1. Obtained in the presence of a very small amount of

When the NCO / OH equivalent ratio is less than 0.5, the unreacted free polyol remains in the derived G prepolymer, so that sufficient homogel strength is not exhibited, and the NCO / OH equivalent ratio is low. When the number exceeds 3, there is no particular adverse effect, but it is disadvantageous in terms of price. Since a certain amount of the isocyanatosilane remains contributes to the decrease in the viscosity of the G prepolymer and is chemically incorporated into the final grout solidified molecule, the NCO / OH equivalent ratio becomes 1 or more.

The G prepolymer adjusted in the above range is:
Most of them are at least 1.2 or more on average in one molecule,
More preferably, an average of two or more dialkoxysilane groups and / or trialkoxysilane groups are introduced into the molecular terminals. There is no problem even if a very small amount of a hydroxyl group remains partially. As a result, in the presence of a curing catalyst, the G prepolymer can easily form a thermosetting gel or a water-insoluble solid easily by contact with moisture and water. To form a prepolymer.

The prepolymer (a), particularly the G prepolymer, of the present invention can be easily obtained generally by a single-step reaction. It may be carried out in the presence of a known catalyst for the purpose of imparting quick-curing suitability of the final grout agent composition and shortening the reaction time, and the soft-combustible phosphate alkyl ester system which is an essential component of the present invention. A plasticizer, or an orthosilicate compound, which is a reactive thickener additionally added as necessary, and other known alkoxymonosilanes other than isocyanatosilane, are allowed to coexist in the reaction system in advance. There is no problem in preparing the solution.

As the catalyst, a known urethane-forming cocatalyst can be selected. Although not particularly limited, for example, an organic tin compound represented by dibutyltin dilaurate or dibutyltin oxide, an organic titanium compound represented by alkyl orthotitanate, other cobalt naphthenate, zinc naphthenate, naphthenic acid There are naphthenic acid transition metal compounds such as lead, octenoic acid transition compounds, and acetylacetone transition metal complexes. In the case of using an organotin-based urethanization-promoting catalyst which is regulated or avoided in the grouting and pouring industry, it is important to make the amount as small as possible.

The grouting agent of the present invention comprises 10 to 200 parts by weight of the flame-retardant alkyl phosphate plasticizer (b) and 100 parts by weight of the prepolymer (a), and further contains an organic acid derived from a natural product (c). ) Is 0.1 to 20 parts by weight, and is a grouting agent which is mentioned as the basic grouting agent of the present invention and which meets the object of the present invention. More preferably, the compounding ratio of the prepolymer (a) and the flame-retardant alkyl phosphate ester plasticizer (b) is (a) :( b)
The weight ratio of (90:10) to (35:65) is generally used, and the range of (75:25) to (50:50) is particularly preferable in terms of securing the flame retardancy and disaster prevention safety. . When the amount of the flame-retardant alkyl phosphate ester plasticizer (b) is less than 10 parts by weight, the viscosity tends to be too high and the infiltration into the ground tends to be difficult, and at the same time, the problem of flame retardancy cannot be solved. On the other hand, if the flame-retardant alkyl phosphate plasticizer (b) exceeds 200 parts by weight, a high-strength gel compact is no longer expected when a grouting agent is used.

As the flame-retardant alkyl phosphate ester plasticizer (b) according to the present invention, known ones can be used and are not particularly limited, but have an affinity with the prepolymer (a). It is necessary to select a material having excellent solubility. Specific examples include, for example, triethyl phosphate, tributyl phosphate, tricresyl phosphate, trioctyl phosphate, and tris-phosphate.
β-chloroethyl phosphate, tris-β-chloropropyl phosphate, tris-β-dichloropropyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, octyl diphenyl phosphate, tris isopropyl phenyl phosphate, and the like, Preferred are tris-β-chloropropyl phosphate and tris-β-chloroethyl phosphate.

The organic acids derived from natural products (c) according to the present invention include, for example, lactic acid, malic acid, and the like.
It may be one selected from tartaric acid, citric acid, abietic acid, natural rosin, phytic acid and its acidic alkali metal salts, and their aqueous dilutions, and also includes enzymatic oxidation products of sugar and glucose. You. In particular, any one of lactic acid, malic acid, tartaric acid, citric acid, abietic acid, and natural rosin, which are easily available on the market, or an aqueous solution of phytic acid may be used as (c). When a water-diluted solution is used as (c), (a) 100
It is important to use the active ingredient so that the solid content of the active ingredient is 0.1 to 20 parts by weight with respect to parts by weight. Phytic acid usually needs to be handled as an aqueous solution in order to ensure its own stability, and more preferably a 5 to 60% by weight aqueous solution is used.

As a natural product-derived organic acid (c), for example, when a 5 to 60% by weight aqueous solution of phytic acid is used, the grouting agent of the present invention is generally solidified (shortened) for a short time by using a small amount thereof. Conclusion). On the other hand, when lactic acid or malic acid is selected as an organic acid (c) derived from a natural product and a small amount thereof is used, the behavior of the grouting agent of the present invention gelling (long-lasting) for about 1 hour is considered. It is mentioned as a characteristic property to show. That is, the gelling behavior of the grouting agent of the present invention can be adjusted to an arbitrary width depending on the organic acid species derived from the natural product and the compounding ratio.

In general, for the purpose of shortening the gelling time of the grout agent of the present invention, other silanol condensation catalysts and water may be used in combination with (c), and may be added and compounded in advance. Can be done. Other silanol condensation catalysts include, for example, alkyl titanates; organosilicon titanates; dibutyltin carboxylate salts such as tin octylate, dibutyltin laurate and malate and fumarate; dibutylamine-2-ethylhexoate Examples thereof include amine salts such as acetate; inorganic acids such as sulfuric acid, phosphoric acid, and hydrochloric acid; and alkaline inorganic compounds such as caustic soda and caustic potash. When using these other silanol condensation catalysts, it is important to determine the amount of the silanol condensation catalyst to be added by performing a sufficient preliminary gelation behavior test and the like. In the present invention, the prepolymer (a) 10
0.001 to 20 parts by weight with respect to 0 parts by weight is good.

As the organic acid (c) derived from the natural product of the present invention, those having excellent compatibility with the above (a) and (b) and promoting uniform curing are selected and used. In addition, since organic acids derived from natural products are widely present in the natural world, they are basically safe and therefore there is no concern about remarkably serious environmental pollution.

In the ground injection using the grouting agent of the present invention, water is indispensable as a hardening component of the prepolymer (a) because a considerable amount of moisture remains on the surface of sand, clay and gravel particles in the ground. Even if is not added and blended in advance, as a result, it comes into contact with ground adsorbed moisture at the time of ground injection, so that there is no hindrance to the essential consolidation reaction. In addition, water may be positively added in advance to the grouting agent of the present invention in advance in order to achieve a more uniform and completely integrated ground consolidated body at an early stage.

When a large amount of water is used, the main components of the present invention sometimes become suspended or finely dispersed in water, but in the present invention, no problem is caused. The amount of water to be added in advance can be freely selected and used within 500 parts by weight based on 100 parts by weight of the prepolymer (a). Although not particularly limited, it is preferably in the range of 1 to 500 mol%, more preferably 50 to 20 mol% based on the molar equivalent of the hydrolyzable group of the active silyl group in the prepolymer (A).
Water can be added and used in the range of 0 mol%, most preferably in the range of 80 to 120 mol%.

For the purpose of promptly providing the gel time or consolidation time after injecting the grout agent of the present invention into the ground, or for the purpose of injecting instantaneously-blocking water corresponding to emergency water stoppage, In the grouting agent of the present invention necessary for coping with construction or the like, it is preferable to use a two-pack type quick-setting grout agent rather than a one-pack type grouting agent. Therefore, the embodiment of the grouting agent of the present invention includes a two-pack type grouting agent.

Specifically, for example, the prepolymer (a) is used as the main component liquid A, and if necessary, another silanol condensation catalyst or a flame-retardant alkyl phosphate-based plasticizer containing water (b) is mixed with a natural resin. A hardener liquid B containing an organic acid derived from a substance or an aqueous solution thereof (c), and a two-pack grouting agent composed of A and B; A mixture of a flammable phosphoric acid alkyl ester-based plasticizer (b) and an aqueous solution (c) of an organic acid derived from a natural product as the curing agent liquid D, or (c) further containing another silanol condensation catalyst as necessary. And a two-pack grouting agent comprising C and D. There is also an example of a two-pack type in which water is added to and mixed with either C or D immediately before use.

More preferably, a liquid obtained by mixing 10 to 100 parts by weight of a flame-retardant alkyl phosphate plasticizer (B) with respect to 100 parts by weight of the prepolymer (A) is used as a base liquid E. On the other hand, raw rosin is added to 100 parts by weight of at least one selected from the following (1) to (3) (1) tris-β-chloropropyl phosphate, tris-β-chloroethyl phosphate, and orthosilicate. A solution containing 0.1 to 20 parts by weight of at least one selected from lactic acid, malic acid, and citric acid, and optionally 0.1 to 10 parts by weight of an organic titanate catalyst, (2 ) 100 parts by weight of at least one selected from tris-β-chloropropyl phosphate, tris-β-chloroethyl phosphate and orthosilicate ester, Chin acid 0.1 to 1
0 parts by weight or a solution containing 1 to 10 parts by weight of one kind selected from rosin, lactic acid, malic acid and citric acid,
(3) Phytic acid and / or an acidic alkali metal salt thereof, or a rosin, lactic acid, malic acid, or a 0.1% by weight aqueous solution of any one selected from citric acid One type is a curing agent liquid F, and the mixing ratio at the time of injection is (100: 1) to (10: 1) in the volume ratio of E liquid: F liquid.
0: 200) is also a preferred embodiment.

The orthosilicate ester is represented by the following general formula (3)

[0056]

The typical one is represented by (RO) ₂ —Si— (OR) ₂ (where R represents any one of a methyl group, an ethyl group, a butyl group, and a propyl group). Preferably, tetramethyl orthosilicate and tetraethyl orthosilicate are mentioned, and their initial condensation products may be used as the viscosity reducing reactive diluent. Especially S
initial condensation products previously prepared as to contain 30 to 45 wt% iO as ₂ minutes are examples of preferred viscosity reducing reactive diluents.

In the grouting agent of the present invention, the following additional components are added in an amount of 0.01 to 10% by weight, preferably 0 to 10% by weight, with particular attention to improvements in workability, penetration rate adjustment, and adhesion improvement. There is no problem even if used within 1 to 3% by weight. For example, light stabilizers represented by hindered amines; hindered phenolic antioxidants; silane coupling agents represented by glycidylsilanes, aminosilanes, mercaptosilanes, vinylsilanes, chlorosilanes; colloidal silica, ultrafine particles Granulated slag, ultra-fine cement, ultra-fine alumina, ultra-fine anhydrous /
Inorganic thixotropy-imparting agents such as hemihydrate / 2-water gypsum powder or inorganic hydraulic particles; peroxide scavengers such as phosphites; inorganic fillers such as charcoal and talc A surfactant or the like can be appropriately added.

Next, a ground injection consolidation method using the grout agent of the present invention will be described. First, as one of the ground injection consolidation methods of the present invention, soft ground in which liquefaction phenomena represented by clay soil, sandy soil, gravel soil, and those composed of composite soil and sinking and settlement are expected. In order to stabilize, the grout agent of the present invention is injected under pressure by a one-shot method, a 1.5-shot method or a two-shot method through an injection pipe buried in the ground to solidify the ground integrally. No.

In the grouting agent of the present invention, (c) in many cases, one shot injection cannot be performed unless the gelation time after addition and blending of the organic acid derived from a natural product is at least 20 minutes or more. Therefore, if solidification or gelation occurs in a shorter time, (a) the main agent liquid and (c)
It is necessary to use a two-shot type with a main curing agent liquid, and to include (b) in either or both of them, and to use it in a 1.5 shot mode or a 2 shot mode.

As a still more preferable ground injection consolidation method of the present invention, liquefaction phenomena represented by clay soil, sandy soil, gravel soil, and composite soils thereof, and sinking and settlement are expected. In order to stabilize the soft ground, first of all, at the beginning of the injection, a flash-set or loose-set relatively high-viscosity selected from the two-pack type of the present invention is introduced through the injection pipe buried in the ground. The drug solution is selected and injected in advance. As a result, the space around the buried tube can be efficiently filled, and a mechanical packer can be easily formed. Next, the long-lasting one-part or two-part type low-viscosity drug solution composition of the present invention is selected and post-injected (including pressure injection) as a post-injection grout drug.
By doing so, the area around the injection tube inserted (approximately radius 0.3
Soft ground in the range of about 2 m) can be infiltrated and consolidated, and the same operation can be repeated in different places to integrate any shape such as pillar, dango or wall into the ground. A ground consolidated reinforcement structure can be formed.

As another example of the ground injection consolidation method of the present invention, in the method of stabilizing soft ground, first, the main constituent components of the present invention are passed through the injection pipe buried in the ground. After injecting a dilute solution of an organic acid from a natural product,
There is a construction method in which the grout agent of the present invention is injected while being pressurized to solidify and solidify the ground.

The grout agent of the present invention is used mainly for the purpose of integrating the back surface of the concrete panel for underground tunnel with the bedrock in contact with the back surface, or integrating the concrete wall of the basement room with the soil in contact with the back surface. Alternatively, it can also be preferably used as a chemical liquid that fills the back surface of a concrete structure under the ground while reinforcing and stabilizing the structure underwater and permanently stopping water. Therefore, the composition of the present invention is provided, for example, to an unstable part or the like existing in the surrounding soil or bedrock on the backside of an underground concrete structure through a hollow anchor bolt material also functioning as a high-pressure injection conduit buried at regular intervals. Can be press-injected and consolidated. That is, as another one of the ground injection consolidation method of the present invention, for an unstable portion at the boundary between the underground concrete and the ground, via a hollow anchor bolt material or the like which also serves as an injection conduit provided at regular intervals,
This is a method of injecting the grout agent of the present invention while applying pressure.

The viscosity at room temperature of the grouting agent of the present invention is BL
Those which exceed 10 ps at 60 rotations measured using a No. 4 rotor with a mold viscometer are not optimal. This is because the grouting agent exceeding 10 ps is too high in viscous resistance and remarkably lacks in ground penetration, and preferably at most 500 cps or less. In particular, in the main grouting agent of the present invention for contributing to infiltration and consolidation other than the use for a packer, the maximum grout is 5 ps or less, preferably 2 ps or less, and most preferably 1 ps or less.

[0064]

EXAMPLES Examples and comparative examples of the present invention are shown below. Parts or% mean parts by weight and% by weight, respectively.
The present invention is not particularly limited by the described embodiments. The production example describes a part of a production example of a prepolymer having an active silyl group terminal which is one of the constituent components. The description of each symbol in the following examples and tables is as follows. PCF; abbreviation of tris-β-chloropropyl phosphate PCE; abbreviation of tris-β-chloroethyl phosphate The various test methods described in each example are as follows.

Flame retardancy test: Hold the end face of the cured body of the grout agent alone (a plate having a thickness of 2 mm, a width of 5 mm and a length of 100 mm) at an angle of 45 ° directly above the oxidation flame of the gas burner.
If the flame spreads within 3 seconds after leaving the flame for 3 seconds immediately after igniting the flame for 3 seconds, it is indicated by the symbol ◎ as having high flame retardancy, and if it disappears within 20 seconds, it is considered to be flame retardant. The symbol "O" indicates that the flame retardancy was slightly lacking within 30 seconds, and the symbol "△" indicates that the flame retardancy was a little poor.

Measurement of gel time (gel time): The time from the point when the curing catalyst solution was mixed with the grout agent composition to the point at which the solution fluidity of the composition itself disappeared at a constant temperature, and the time was 1 minute. Those that are within are displayed as [intermediate], those within 1 to 5 minutes are displayed as [intermediate], those within 5 to 30 minutes are displayed as [intermediate], those that are 30 minutes to less than 2 hours are [long] ]. Also, it takes 2 hours to 1 day and night.
Displayed.

Uniaxial compression test: A method in accordance with JIS-A-1216, and was performed at a compression speed of 1.5 mm / min using an SG-2033B electric uniaxial compression tester manufactured by Maruto Seisakusho.

Measurement of homogel strength and its strain rate: The physical properties of a cured product of the grout agent composition alone.
After obtaining a columnar homogel cured product having a height of mm, the above-mentioned uniaxial compressive strength is obtained and the value is defined as the homogel strength. Further, a value obtained by dividing the amount of deformation up to breakage at the time of uniaxial compression measurement by the original height and multiplying by 100 was displayed as a strain rate (%).

Sandgel strength; 38.5 to grout agent
40.5vol% and 59.5-61.5v of Toyoura standard sand
ol% is uniformly mixed, packed in a mold container so as to prevent air bubbles from entering, solidified, cured, and demolded to obtain a columnar cured sandgel having a diameter of 50 mm and a height of 100 mm. The value of the uniaxial compression strength of the sand gel is defined as the sand gel strength.

Penetration suitability test: A transparent acrylic filling tower having an opening hole on each of the upper and lower sides and having a diameter of 10 cm was prepared, and Toyoura standard sand was finely packed in the presence of water so that the filling height was 1 m. When each grout agent of each Example and Comparative Example was respectively injected at an injection pressure of 1.5 kg / cm ² from the opening at the top of the packed tower, the injection permeation rate (200 to 210 ml / min) using only city water was 100. Infusion rate ratio of each grout agent to water is 70%
The cases where the above-mentioned conditions and inter-particle infiltration and consolidation are possible are indicated by the symbol ◎. In addition, the injection / penetration rate ratio to water is 50 to 70%.
Symbol when the infiltration and consolidation between particles are possible, symbol of ○, when the infiltration speed ratio to water is 15 to 50%, and when permeation and consolidation between particles is possible, and 15% or less. The cases were indicated by x symbols.

Endurance test: either a columnar homogel or a cured sandgel obtained by the above method was immersed in a flowing water displacement water tank set so that 10 liters would be replaced once a day and night, for a certain period of time. The results of observing the uniaxial strength retention% and the change in appearance at that time were shown as results of a water resistance durability test (hereinafter, referred to as a durability test 1). On the other hand, a seawater immersion durability test result was prepared by preparing an artificial seawater solution defined by JIS, immersing the artificial seawater in the artificial seawater for a certain period of time, and maintaining the uniaxial compressive strength (hereinafter referred to as durability test 2). ).

Production Example 1 A 1-liter four-necked reaction flask equipped with a reflux condenser was prepared, and a polyether polyol having a weight average molecular weight calculated from a hydroxyl value of 2,000 and a hydroxyl value of 56 mgKOH / g was prepared. 500 parts of polypropylene glycol (0.50 mol / active OH equivalent), 105 parts of γ-isocyanatopropyltrimethoxysilane (0.502 mol / active NCO equivalent) and 0.1 part of acetylacetone aluminum complex as a catalyst The reaction mixture was charged at 110 ° C. for 5 hours in a nitrogen stream, cooled, and cooled to 0% according to the NCO group-containing quantitative analysis result by the dibutylamine solution method.
%, And a prepolymer 1 having 100% of a hydrolytically active silyl group introduced into the terminal of the polyether main chain having a molecular weight of 2,000 was obtained. The solution viscosity of the prepolymer 1 alone at 25 ° C. by a B-type viscometer was 541 cps. After adding 0.01 part of dibutyltin dilaurate to 10 parts of this prepolymer 1 to obtain a moisture-curable single prepolymer liquid, a 2 mm-thick moisture-cured film was prepared, and the strip film was used. Transition temperature (Tg) of the polyether main chain measured by the penetration method performed in
3 ° C.

Production Example 2 In the same manner as in Production Example 1, the weight average molecular weight was 3,060,
Polyether triol having a hydroxyl value of 55 mgKOH / g (addition molar ratio of ethylene oxide (EO) to propylene oxide (PO) is 15:85)
0 parts (0.490 mol / active OH equivalent) and 122 parts of γ-isocyanatopropyltriethoxysilane (0.4 parts
91 mol / active NCO equivalent) and 0.01 part of dibutyltin oxide as a catalyst.
After reacting at 0 ° C. for 2 hours, the mixture was cooled and almost quantitatively obtained Prepolymer 2 having a molecular weight of 3,060 / polyether main chain having a hydrolytically active silyl group terminal. The solution viscosity of the prepolymer 2 alone at 25 ° C. by a B-type viscometer was 930 cp.
s. The result of Tg measurement of the polyether main chain carried out in the same manner as in Production Example 1 was about -60 ° C.

Production Example 3 In the same manner as in Production Example 2, except that the charged amount of γ-isocyanatopropyltriethoxysilane was changed to 244 parts, water was almost quantitatively added to the polyether main chain having a molecular weight of 3,060. Decomposition-active silyl group-terminated resin precursor 83.6
% And unreacted γ-isocyanatopropyltriethoxysilane 16.4%. The solution viscosity of the prepolymer 3 alone at 25 ° C. by a B-type viscometer was 580 cps.

Production Example 4 Prepolymer 4 was obtained in the same manner as in Production Example 2 except that γ-isocyanatopropyltriethoxysilane was used in an amount of 82 parts.

Production Example 5 Prepolymer 5 was obtained in the same manner as in Production Example 2, except that 103 parts of γ-isocyanatopropyltrimethoxysilane were used instead of γ-isocyanatopropyltriethoxysilane. The solution viscosity of prepolymer 3 alone at 25 ° C. by a B-type viscometer was 900 cps.

Preparation Example 6 In Preparation Example 1, the polyether polyol was prepared by mixing polypropylene glycol having a weight average molecular weight of 400
3.3 parts, 66.7 parts of a polypropylene glycol having a weight average molecular weight of 700, and a total average hydroxyl number of 22
500 parts (1 mol / mol) of 4.4 mg KOH / g mixed polypropylene glycol (total average weight average molecular weight: 500)
(Active OH equivalent), 209 parts (1 mol / active NCO equivalent) of γ-isocyanatopropyltrimethoxysilane and 0.3 part of an acetylacetone aluminum complex as a catalyst were charged and reacted at 120 ° C. for 5 hours in a nitrogen stream. After cooling, 0% was confirmed by the NCO group-containing quantitative analysis result by the dibutylamine solution method, and a prepolymer 6 having 100% of hydrolytically active silyl groups introduced into the terminal of the polyether main chain having an average molecular weight of 500 was obtained. . The solution viscosity of prepolymer 6 alone at 25 ° C. by a B-type viscometer was 415 cps.

Production Example 7 The polyether polyol used in Production Example 1 had a weight average molecular weight of 8,415 and a hydroxyl value of 12 mgKOH /
g of 500 g of a polyether-based triol (addition molar ratio of ethylene oxide (EO) to propylene oxide (PO) is 15:85), 22.2 parts of γ-isocyanatopropyltrimethoxysilane, and 0.1 g as a catalyst. Charge with 3 parts of acetylacetone aluminum complex,
After reacting at 120 ° C. for 5 hours in a nitrogen stream, the mixture was cooled to obtain a prepolymer 7 having a polyether main chain having an average molecular weight of 8,400 and having hydrolytically active silyl groups introduced therein.

Production Example 8 In the same manner as in Production Example 1, the weight average molecular weight was 1,065,
532 parts of polybutadiene polyol having a hydroxyl value of 105.5 mgKOH / g and 209 parts of γ-isocyanatopropyltrimethoxysilane (1 mol / active NCO equivalent)
Then, 0.1 part of an acetylacetone copper complex was charged as a catalyst, reacted at 110 ° C. for 3 hours in a nitrogen stream, cooled, and confirmed to be 0% by NCO analysis using a dibutylamine solution method, and the main chain of the polybutadiene skeleton was confirmed. To obtain a prepolymer 8 having a hydrolytically active silyl group as a functional group. The solution viscosity of the prepolymer 8 alone at 25 ° C. by a B-type viscometer was 2,658 cps. The Tg measurement result of main chain polybutadiene performed in the same manner as in Production Example 1 was approximately −
It was 50 ° C.

Production Example 9 The prepolymer 8 obtained in the same manner as in Production Example 8 was hydrogenated in the presence of a palladium carbon hydrogenation catalyst, and the decatalyzed solution resin was used as prepolymer 9.

Production Example 10 Production of Prepolymer 10 In the same manner as in Production Example 1, the weight average molecular weight was 1,520,
500 parts of hydrogenated polyisoprene polyol having a hydroxyl value of 74.1 mgKOH / g, 143 parts (0.657 mol / active NCO equivalent) of γ-isocyanatopropyldiethoxymethylsilane, and 0.1 part of acetylacetone copper complex as a catalyst And reacted at 100 ° C. for 2 hours in a nitrogen stream, and then cooled.
O analysis confirmed 0%, and a prepolymer 10 having a hydrolytically active silyl group as a functional group in the main chain of the hydrogenated polyisoprene skeleton was obtained. The solution viscosity of the prepolymer 10 alone at 25 ° C. by a B-type viscometer was 3,170 cps.

Production Example 11 A 1-liter four-necked reaction flask equipped with a reflux condenser was prepared, 306 parts of 2-hydroxyethyl disulfide was charged into the flask, and the flask was heated to 100 ° C. in nitrogen.
There, 6.2 of 2,2'-azobisisobutyronitrile
What melt | dissolved 8 parts in 130 parts of n-butyl acrylate was dripped over 30 minutes. The reaction temperature during dropping is 10
The temperature was adjusted to 0 to 105 ° C., and after the completion of the dropwise addition, the polymerization reaction was continued for 30 minutes, followed by cooling to room temperature. The cooled reaction solution was transferred to a separatory funnel, 200 parts of toluene was added, the mixture was shaken vigorously and allowed to stand, and the supernatant was collected.
After adding 0 parts and performing deionization treatment twice, toluene was removed using a vacuum evaporator to obtain a solution-type polybutyl acrylate resin composition. The weight average molecular weight by gel permeation chromatography of this resin solution in THF solvent was about 2,190 in terms of polystyrene, and the average OH was
It was a telechelic liquid acrylic polyol (hereinafter abbreviated as AP-1) into which two groups were introduced.

For 100 parts of AP-1, 28.6 parts of γ-isocyanatopropyltrimethoxysilane (1.
(Equivalent to 5 times molar equivalent / OH equivalent) and 0.1 part of acetylacetone aluminum complex as a catalyst, reacted at 120 ° C. for 3 hours in a nitrogen stream, cooled, and analyzed for NCO by a dibutylamine solution method. Confirm 0% with A
A prepolymer 11 having hydrolytically active silyl groups as both terminal functional groups of the P-1 skeleton main chain was obtained. The solution viscosity of the prepolymer 11 alone at 25 ° C. by a B-type viscometer was 870
cps. This prepolymer is a viscous liquid at room temperature, and thus the Tg of the main chain polymer is 20 ° C. or less.

Production Example 12 A 1-liter four-necked reaction flask equipped with a reflux condenser was prepared, and 100 parts of methyl cellosolve was charged into the flask, and heated to 100 ° C. in nitrogen. Separately from a solution containing 256 parts of n-butyl and 8.5 parts of hydroxyethyl methacrylate, 150 parts of methyl cellosolve and 2,2′-azobis [2-methyl-N- (2
-Hydroxyethyl) propionamide] was separately dropped quantitatively over 3 hours. After the dropwise addition, the remaining monomer was allowed to undergo a polymerization reaction for 1.5 hours, and further reacted at 120 ° C. for 30 minutes, and then cooled to room temperature. The polymerization solution was further detoluened with a vacuum evaporator to obtain a solution-type polybutyl acrylate resin composition. The resin solution was subjected to gel permeation chromatography using a THF solvent to give a weight average molecular weight of about 3,800 in terms of polystyrene, and a liquid acrylic polyol (hereinafter referred to as AP-2) having an average of 1.9 OH groups introduced per molecule. Abbreviated).

For 100 parts of AP-2, γ-isocyanatopropyltrimethoxysilane was added to 20. 9 parts (amount equivalent to 1 molar equivalent / OH equivalent) and 0.1 as a catalyst
Part of acetylacetone aluminum complex was charged, reacted in a nitrogen stream at 120 ° C. for 3 hours, cooled, and 0% was confirmed by NCO analysis using a dibutylamine solution method.
A prepolymer 12 having hydrolytically active silyl groups as both terminal functional groups of the skeleton main chain was obtained. The solution viscosity of prepolymer 12 alone at 25 ° C. by a B-type viscometer was 1,770 cp.
s.

Examples 1-5 Solutions A and B were prepared from prepolymers 1 and 2, tris-β-chloropropyl phosphate, and a 50% aqueous solution of phytic acid derived from natural products in the proportions shown in Table 1 below. After mixing and homogenization, grouting agents A1 and A2 (Examples 1 and 2) and B
1 to B3 (Examples 3 to 5) were prepared. No. in BL type viscometer. Viscosity measurement value at the time of mixing preparation of A and B when 3 rotors were used.
Table 1 shows the measurement results of the uniaxial compressive homogel strength and the uniaxial compressive strength of the sandgel after pouring into a cylindrical mold container having a length of m and forming a homogel body and then left and cured for one day. Further, a homogel body that had undergone aerial curing for 5 days after gelation in Example 1 and Example 3 was prepared, immersed in non-running water having a volume 5 times the gel volume for 10 days, and collected in immersion water. Showed only a very small amount of alcohol and phytate derived from natural products, which were far below the water quality standard value, but did not show any significant water pollution.

Comparative Examples 1-4 Grout suitability of a grout composition prepared by mixing and homogenizing agents A and B shown as V1 to V4 in Table 2 using prepolymer 1 or prepolymer 2 Was measured. As is clear from the results of V1 to V3 in Table 2, when the flame-retardant plasticizer was not added or only a small amount was added, the cured homogel having a gel time behavior of instantaneous setting or middle setting and having a transparent homogelling property was obtained. Although the product was produced, the flame retardant test result of the cured product was a flammable solid, so the grouting agent composition itself was significantly lacking in flame retardancy, and the danger of igniting or burning fire upon injection was apparent. And lacked suitability for a highly safe grouting agent. On the other hand, as is clear from the results of V4 in Table 2, when the flame-retardant plasticizer is added and blended in an unnecessarily large amount, the homogel strength is low, and the homogel of a general water glass grout agent is used. The fact that the strength did not exceed and the bleeding of the flame retardant plasticizer were remarkable.

Examples 6 to 12 Each of the prepolymers obtained in Production Examples 3 to 9, PCF and / or PCE, and organic acids derived from natural products, etc., as shown in Table 3, were used as a base agent E solution and a curing agent F solution, respectively. After adjusting and blending uniform
Each grout agent composition of C1 to C7 was obtained and subjected to a grout suitability test. The results are shown in Table 3.

Examples 13-17 Each of the prepolymers obtained in Production Examples 10-12, PCF, and organic acids derived from natural products, etc. were used as base agent liquids G as shown in Table 4.
And the curing agent liquid H were adjusted and mixed and homogenized to obtain grout agent compositions C8 to C12, which were subjected to a grout suitability test.
The results are shown in Table 4.

Examples 18 to 22 Prepolymers 1, 2, and 11, PCF, organic acids derived from natural products, and the like were prepared in one solution as shown in Table 5, and immediately subjected to various tests. Table 5 also shows the adjusted test results of the grout agent numbers C13 to C17.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

[Table 3]

[0094]

[Table 4]

[0095]

[Table 5]

Example 23 Using the grout agent of Example 18 and a single shot system through a grout-injected single tube, the discharge pressure was 2.5 kg / cm.
Injected into river sand ground having an average particle diameter of 350 μm in ² ,
Infiltration into a range of approximately 1 m in diameter and 3 m in depth. After 7 days, the sample was dug out, and the center of the consolidation part and the sandgel core (50 mmφ × 100 mmH) at the position 50 cm left and right were sampled, and the uniaxial compressive strength was measured.
kgf / cm ² , and was found to be uniformly consolidated. The strain rate at the time of the fracture in the test was 14 to 15%, which was rich in elasticity.

Further, it was found that the permeability of the sand gel core collected from the vicinity thereof was 2.2 × 10 ⁻⁵ cm / sec, which was excellent in waterproofness and was improved to the reinforced stabilized ground. Similarly, an appropriately collected sandgel core of the same size was stored in running water for one month and tested for water resistance. As a result, the strength was maintained at 98% or more, and no change in appearance was observed. Similarly, after immersing the appropriately collected sand gel core of the same size in non-running water having a volume 5 times the core volume for 10 days, trace amounts of alcohol and the like far below the water quality standard value are recognized in the immersion water collected. No significant water pollution was observed.

Example 24 The two-pack main agent type grouting agent of Example 4 (grouting agent No. B
By using 2), the base liquid and the hardener liquid are separately supplied at a weight ratio of 1: 1 by a liquid sending pump, and the two liquids are impact-mixed and homogenized near the inlet of the grout single pipe. Through a grouting unit and a grouting single tube, the material is injected into a river sand layered ground having an average particle diameter of 350 μm under a discharge pressure of 2 kg / cm ² by a so-called 1.5 shot method under a discharge pressure of 2 kg / cm ^2. To a range of 3 m. After 7 days, the center of the consolidation part and the sandgel core (50 mmφ × 100 mmH) at the position 50 cm left and right were sampled and the uniaxial compressive strength was measured. As a result, each was 13 ± 1 kgf.
/ Cm ² and found to be uniformly consolidated. The strain rate at the time of fracture in the test was also 9 to 10%, which was rich in elasticity.
It was also found that the permeability of the sandgel core collected from the vicinity was 1.6 × 10 ⁻⁵ cm / sec, indicating that the sandgel core had been improved to a reinforced stabilized ground with a high waterproofness. Similarly, an appropriately collected sand gel core of the same size was stored in running water for one month and tested for water resistance. As a result, no decrease in strength was observed and no change in external dimensions was observed.

Example 25 Five liters of base solution K containing 90% of prepolymer 2 and 10% of PCF, and 50 parts of hardener solution L containing 90% of PCF and 10% as a 50% aqueous phytic acid solution Liters were prepared in separate tanks, respectively, and the two-liquid mixed type grouting agent was supplied to a single grout double tube at a volume ratio of 1: 1 by a separate liquid sending and measuring pump installed under each tank, The so-called two-shot system in which the two liquids are impact-mixed and homogenized at the tip of the single grout tube and injected into the ground has an average particle diameter of 200 under a discharge pressure of 1 kg / cm ^2.
The entire volume was injected into an unstable ground where a μm river sand and a few centimeters of gravel layer were complexly stacked. As a result of digging out the compact two days later and observing the compact, the grout was found to be a composite compact mainly including a gap around the outer periphery of the injection pipe and a gravel layer. In addition, 20 of the liquid discharged by the same device and system
As a result of measuring the gel time at room temperature and at room temperature, the result was about 40 seconds, and it could be said that this was a quick-setting grouting agent.

Example 26 A 50 mm thick concrete plate in which a hollow anchor bolt having a diameter of 15 mm and a grouting agent capable of being grouted by a 1.5 shot system and a grouting tube serving as a grouting tube were set at the center was used. There is 2 in 25cmφ around the center
There is a through crack having a width of 0.3 mm and a length of 5 cm, and a steel funnel having a size of 25 cmφ is adhesively sealed on the back surface of the crack to allow tap water to leak at a pressure of 5 kg / cm ² . Example 2 for the water leakage model wall
A grout having the same composition as that shown in No. 5 was injected at a discharge pressure of 75 kg / cm ² by a 1.5 shot injection method. As a result, 7 seconds after the start of the discharge, the grout agent began to flow out of the crack penetrating site, and at the same time became thickened and gelled, and all the water leaking sites stopped completely within about 2 minutes. This result indicates that it can be a grouting agent for emergency water stoppage.

[0101]

As is apparent from the examples, the grouting agent of the present invention is an organic polymer grouting agent which has been a concern and has high elasticity and long-term durability, and has the following convenience. It has an effect. That is, the grouting agent of the present invention can improve soft ground to a soil with high durability and durability. In addition, the main ingredient is composed mostly of liquid components, and any gel time such as high permeability and instantaneous or slow setting can be easily adjusted. The final injected solidified body (homogel and sandgel) has high toughness. Rich and high compressive strength stability can be secured for a long time. Further, basically, it is easy to handle and administer the injection with one liquid, and the flame retardancy ensures the safety of the injection work site. Further, it is possible to provide an organic polymer grouting agent which has a property of gelling and consolidating upon contact with water present in the ground and is free from the contamination of groundwater elution of its main component. Furthermore, the water-permeability of the injection | pouring solidification is extremely small, and the water stopping effect is high.

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Claims (12)

[Claims] (1) Formula (1) showing the property of crosslinking with siloxane by hydrolysis:-(CH ₂ ) ₃ -Si (R ¹ ) _n- (X) _3-n (1) (where R ¹ Is a chlorine atom, a hydrogen atom, a methyl group, an ethyl group or a propyl group, X is an alkoxyl group, an oxime group or an acetoxyl group having 1 to 5 carbon atoms, and n is 0 or 1.) It has at least 1.2 or more terminal groups per molecule on average, and the glass transition temperature of the organic polymer long chain of the main chain excluding its active silyl group is 2
0 ° C. or lower and weight average molecular weight of 500 to 20,000
Of the flame-retardant alkyl phosphate plasticizer 10 per 100 parts by weight of the active silyl group-containing prepolymer in the range of
A permanent and elastic organic polymer-based soil-improving injectable consolidation agent comprising -200 parts by weight and 0.1-20 parts by weight of an organic acid derived from a natural product. 2. An active silyl group-containing prepolymer, wherein R ^{1 in the} formula (1) is a methyl group or an ethyl group, and X is a carbon atom having 1 carbon atom.
5 to 5 having an average of at least two active silyl group terminals per molecule, and having a glass transition temperature of 0 ° C. of the organic polymer long chain of the main chain excluding the active silyl group.
And the weight average molecular weight is in the range of 1,000 to 5,000, and the flame-retardant alkyl phosphate plasticizer is contained in an amount of 30 to 100 based on 100 parts by weight of the active silyl group-containing prepolymer. The injection consolidation agent for ground improvement according to claim 1, wherein the organic acid derived from a natural product is 1 to 10 parts by weight. 3. The prepolymer liquid containing an active silyl group has a total weight average hydroxyl value of 10 to 450 mg KOH /
g at room temperature and a polyol which is liquid at room temperature and has the following formula (2): OCN-R ² -Si (R ¹ ) _n- (X) _{3 -n} (2) (where R ² is An alkylene group having 3 or more carbon atoms, R ¹
Represents a methyl group, an ethyl group or a propyl group, and X represents 1 carbon atom.
To 5 alkoxyl groups, n represents 0 or 1. 3. The injection for ground improvement according to claim 1 or 2, which is obtained by reacting the isocyanate silane represented by the formula (1) with an NCO / OH equivalent ratio in the range of 0.5 to 3.0. Caking agent. 4. The polyol is a diol or triol which is liquid at ordinary temperature and has a total weight average hydroxyl value in the range of 25 to 300 mg KOH / g, and the NCO / OH equivalent ratio is in the range of 0.95 to 1.05. 3. The injection consolidating agent for ground improvement according to 3. 5. The isocyanate silane is selected from γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyldiethoxymethylsilane, γ-isocyanatopropyldimethoxymethylsilane. The injection consolidating agent for soil improvement according to claim 3 or 4, wherein the agent is one type. 6. The polyol is at least one or more selected from the following polyols (a) to (e) which are liquid at ordinary temperature and have a total weight average hydroxyl value in the range of 20 to 350 mg KOH / g. Item 4. An injection consolidating agent for ground improvement according to Item 3. (A) Polyether polyol (b) Telechelic acrylic polyol (c) Polyisoprene polyol and / or hydrogenated product thereof (d) Polybutadiene polyol and / or hydrogenated product thereof (e) Silicon polyol 7. The method according to claim 1, wherein the soft-flammable alkyl phosphate ester plasticizer is tris-β-chloropropyl phosphate or tris-β-chloroethyl phosphate. The injection consolidating agent for soil improvement according to the above. 8. The organic acid derived from a natural product is at least one selected from lactic acid, malic acid, tartaric acid, citric acid, abietic acid and natural rosin. The injection consolidating agent for ground improvement according to claim 1. 9. The injection consolidating agent for soil improvement according to claim 1, wherein the organic acid derived from a natural product is phytic acid and / or an acidic alkali metal salt thereof. 10. In a method for stabilizing soft ground, a one-shot method, a 1.5-shot method is used through an injection pipe buried in the ground.
10. A ground injection consolidation method for injecting the agent according to any one of claims 1 to 9 while applying pressure by any one of a shot method and a two-shot method to stabilize the ground. 11. A method for stabilizing soft ground, wherein a dilute solution of an organic acid derived from a natural product is first injected through an injection pipe buried in the ground. A ground injection consolidation method, which comprises injecting the agent according to claim 1 while applying pressure. 12. The method according to claim 1, wherein an unstable portion at a boundary portion between the underground concrete and the ground is provided via a hollow anchor bolt material serving also as an injection conduit provided at regular intervals.
A ground injection consolidation method characterized by injecting the agent according to any one of the above, while applying pressure.