JP4848293B2 - Ultra-fine particle injection material composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultrafine particle grout composition which is excellent in dispersibility and dispersion retainability and can be easily injected into minute spaces between particles of grounds, rock cracks, and the like, and a method for manufacturing such ultrafine particle grout composition. <P>SOLUTION: The ultrafine particle grout composition comprises mixing ultrafine particle cement containing (a) 2 to 25mass% cement clinker of 5mass% in the content of 3CaO-Al<SB>2</SB>O<SB>3</SB>, (b) 74 to 97mass% blast furnace slag and (c) 1 to 5mass% gypsum, and 60 to 80vol.% in the particle volume of a grain size 1 to 5 &mu;m in powder and polycarboxylic acid-based dispersant as essential components. The method for manufacturing the ultrafine particle grout composition has a high-speed stirring step of performing mixing and stirring with &ge;314 m/min of peripheral speeds, then mixing and stirring the ultrafine particle cement and water as essential components and has a step of further adding water and restirring the mixture. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

The present invention relates to an ultra-fine particle injection material composition and a method for producing the same. More specifically, it is a slurry-like injection material containing cement composed of ultra-fine particles having an extremely small particle size, and is used for improvement, water stoppage, etc. by injecting into the ground or rock in the field of civil engineering and construction. The present invention relates to an injection material composition and a method for producing the same.

The injection material composition containing cement particles is used by injecting into the ground particle gaps and rock cracks in order to stop water, prevent liquefaction, improve soft ground, and prevent leakage of harmful substances. Widely used in foundation construction. For example, it is used for ground reinforcement and water stoppage during construction of dams, tunnels, subways, and water and sewage systems. As such a cement type injection material composition, a cement type injection material mixed with water and stirred to form a slurry is used. In this case, a dispersant is used in order to improve the dispersibility of cement particles and improve the performance as an injection material composition, and a slurry obtained by mixing and stirring a cement-based injection material, a dispersant, and water is used. Examples of the cement-based injection material include ordinary Portland cement, early-strength Portland cement, blast furnace cement, colloidal cement, and ultrafine particle cement. In the performance of the cement-type injection material composition, the particle size of the cement-type injection material is important. Generally, the injection property is improved by reducing the particle size. Among cement-based injecting materials, ultrafine cement is the most excellent injectability and has many practicalities.

As a conventional ultrafine cement-based injection material, Portland cement or a mixture of Portland cement clinker (hereinafter referred to as cement clinker), blast furnace slag, and gypsum having a maximum particle size of about 10 to 16 μm is used.
Furthermore, in order to improve the dispersibility and reduce the coarsening of apparent particles due to aggregation, ultrafine particle cements having a specific particle size range limited to a particle amount of about 2 μm or less are known (for example, patents). Reference 1). Ultrafine cement with such a specific particle size range has improved injectability compared with conventional ultrafine cement, but depending on the particle gap and rock cracks to be injected, In some cases, injection was not possible. Therefore, there has been a demand for an ultra-fine cementitious injection material composition that is excellent in injectability and can be applied to various forms of ground and rock.

Also, in the case of ultrafine cement with a particle size smaller than necessary, for example, when the particle size is smaller than that of ultrafine cement such as ultra-fine cement, there is a strong agglomeration effect, and even in a dry state, Agglomeration is observed in the meantime, and the phenomenon that the agglomeration speed in the slurry is extremely fast is recognized. For this reason, the dispersion of the particles in the slurry is likely to be insufficient, and the coarsening of the apparent particles due to aggregation is accelerated. When such a slurry is used as an injection material, the injection property is rather deteriorated (see, for example, Non-Patent Document 1).

From such a background, for the purpose of improving the dispersibility of cement particles and improving the injectability, a high-pressure dispersion treatment method (for example, see Patent Document 2) or a method for removing aggregated particles after ultrasonic treatment (for example, Patent Document 3) is known. However, in these methods, a special apparatus is required and the production line becomes complicated, and since reaggregation is easy after the particle dispersion treatment, the dispersion retention property and the like are improved, and the injection property is increased. There was room for ingenuity. Further, in the method of removing the aggregated particles after the ultrasonic treatment, a slurry to be discarded is generated, and the injection efficiency is inferior. Therefore, there is a demand for practical use of an injection composition using an ultra-fine particle cement injection material that is expected to have extremely high injection properties, and the dispersibility of the ultra-fine particle cement injection material by an industrially simple method. In addition, there is room for improvement in order to improve the dispersion retention and to improve the injection efficiency.
Japanese Patent No. 3423913 JP-A-3-26783 JP 2000-70700 A Mori Kaoru, Tamura Masahito, Aoki Koji, "Limit of Permeation of Ultrafine Particle Injection Material", Proceedings of Japan Society of Civil Engineers, No.426 / V-14, pp237-240, (1991.2)

The present invention has been made in view of the above-mentioned present situation, is excellent in dispersibility and dispersion retention, and is extremely fine ground that cannot be injected due to the size of the particle diameter with the conventional ultrafine cementitious injection material. Ultra-fine particle injection material composition that can be easily injected into particle gaps, rock cracks, etc., and production of such ultra-fine particle injection material composition without the need for special equipment or production line It is an object to provide a method for doing this.

As a result of various studies on the ultra-fine particle injection material composition, the present inventors have found that a polycarboxylic acid-based dispersant is essential in the ultra-fine particle injection material composition including the ultra-fine particle cement whose component and composition are specified. When included as a component, it is possible to reduce the agglomeration of cement particles as much as possible due to the excellent dispersion effect of the polycarboxylic acid-based dispersant, so that it exhibits excellent injectability that surpasses conventional ultrafine cement. I found out. In addition, the ultra-fine particle injection material composition can be produced by a production method having a high-speed stirring step of mixing and stirring at a specific rate in the presence of a polycarboxylic acid-based dispersant, or a two-stage water stirring method of adding and stirring twice or more. It has been found that an ultra-fine particle injection material composition excellent in dispersibility and dispersion retention can be obtained by manufacturing, and can be suitably used for injection applications. In addition, since such a manufacturing method does not require a special apparatus, it has been found that the ultra-fine particle injection material composition can be easily and inexpensively manufactured, and it has been conceived that the above problems can be solved brilliantly. .

That is, the present invention includes (a) 2-25% by mass of cement clinker in which the content of 3CaO.Al ₂ O ₃ is 5% by mass or less, (b) 74-97% by mass of blast furnace slag, and (c) gypsum 1-5. Ultra-fine particle injection material composition comprising, as essential components, an ultra-fine particle cement and a polycarboxylic acid-based dispersant containing 60% by volume of particles having a particle size of 1 to 5 μm in powder. It is a thing.
Moreover, the preferable form in the ultra-fine particle injection material composition of the present invention is that the polycarboxylic acid dispersant is derived from a repeating unit derived from an unsaturated polyalkylene glycol monomer and an unsaturated carboxylic acid monomer. And a polycarboxylic acid copolymer having a repeating unit.
The present invention is also a method for producing the ultra-fine particle injection material composition described above, wherein the production method comprises an ultra-fine particle injection material composition having a high-speed stirring step of mixing and stirring at a peripheral speed of 314 m / min or more. It is also a manufacturing method.
The present invention further relates to a method for producing the ultra-fine particle injection material composition described above, wherein the production method comprises a step of mixing and stirring with ultra-fine particle cement and water as essential components, and further adding water and re-stirring. It is also a method for producing an ultra-fine particle injection material composition.
The ultrafine particle injection material composition includes various forms such as a solid (powder) and a liquid (slurry). Usually, an ultrafine particle cement, a polycarboxylic acid dispersant and water are essential components. It is used as an ultra-fine particle injection material composition that is mixed as follows. In this case, the slurry is in a form, and such a slurry is also referred to as “ultrafine particle cement grout slurry” or simply “slurry”.
The present invention is described in detail below.

The ultra-fine particle injection material composition of the present invention is obtained by mixing an ultra-ultra fine particle cement having a specified component and composition and a polycarboxylic acid dispersant as essential components.
In the present invention, the ultra fine particle cement is one in which the amount of particles having a particle diameter of 1 to 5 μm in the powder is 60 to 80% by volume. The ultra-fine particle cement used in the ultra-fine particle injection material composition of the present invention is such that the components and composition are specified in this way. When the ultra-fine particle cement contains the above-mentioned particle size in the above-described particle amount, the obtained ultra-fine particle injection material composition can exhibit excellent injectability. The range in which the amount of particles having a particle size of 1 to 5 μm in the powder is 60 to 80% by volume is a finer powder than that of conventional ultrafine cement and has a particle size that can be industrially produced. When the amount of particles having a particle size of 1 to 5 μm in the powder of the above ultra-fine particle cement is less than 60% by volume, the particle size is the same as that of the conventional ultra-fine particle cement system, and excellent injectability is not sufficiently exhibited There is a fear. On the other hand, if it exceeds 80% by volume, there is a limit in removing particles of 1 μm or less with the current production technology, which may be difficult to achieve industrially, and 80% by volume is the upper limit. . The particle amount of 1 to 5 μm is more preferably 60 to 75% by volume, and still more preferably 65 to 75% by volume.

The amount of the particles is preferably measured after treatment for 3 minutes with an ultrasonic cleaner (output 40 W, frequency 40 kHz) using, for example, ethanol as a dispersion medium.
The above-mentioned particle amount represents the particle amount in the range of 1 to 5 μm in the particle size contained in the ultra-fine particle cement, and is a laser diffraction particle size distribution analyzer (SALD-2000J, Shimadzu Corporation, refractive index 1.70 ± 0.20i ), The amount of particles of the powdery ultra-fine particle cement can be measured. The amount of particles having a particle size of 1 to 5 μm in the powder thus obtained is set to 60 to 80% by volume.

In the ultra-fine particle injection material composition of the present invention, as the cement clinker, the content of 3CaO.Al ₂ O ₃ (hereinafter also referred to as C3A) is sufficient for the effect of the present invention with respect to 100% by mass of the cement clinker. In order to express it in 5 mass% or less. By setting the content to 5% by mass or less, the injection property of the ultrafine particle injection material composition can be made sufficiently excellent, and particularly good initial injection property can be obtained. The content of C3A is more preferably 2 to 5% by mass. More preferably, it is 3-5 mass%. In addition, content of C3A can be calculated | required from a Borg type | formula.

The cement clinker in the present _{invention, 3CaO · SiO 2, 2CaO ·} SiO 2, 3CaO · Al 2 O 3 ( also referred to as C3A.), Is intended to include as the major mineral _{4CaO · Al 2 O 3 · Fe} 2 O 3. Cement clinker differs greatly in hydration activity, grindability and the like by changing the content of these minerals. The content of these minerals is not particularly limited as long as the effects of the present invention are exerted, but among these minerals, C3A has a higher adsorption amount of the dispersant than other minerals, so the C3A content is reduced. By doing so, the initial dispersant concentration in the slurry liquid can be maintained high, and the dispersion retention of the ultra-fine particle injection material composition can be increased. C3A has a high initial hydration activity, and in addition to promoting particle aggregation, it reacts rapidly with gypsum to produce ettringite (3CaO · Al ₂ O ₃ · 3CaSO ₄ · 32H ₂ O), which is the initial hydrate of injection inhibition. It is known to do. Also, C3A segregates to the fine powder side during pulverization, and if the cement clinker is made higher powder, the number of ultrafine C3A particles increases remarkably, and the high dispersibility and high dispersion retention of the ultra-fine particle injection material composition are sufficient. Therefore, it is preferable to reduce the content.

The cement clinker is not particularly limited as long as C3A is a cement clinker within the above-mentioned range, and specifically, it is a cement clinker belonging to the categories of sulfate-resistant cement, medium heat cement, and low heat cement as defined in JIS. It is preferable. More preferably, it is a cement clinker belonging to the category of medium heat cement and low heat cement.

In the ultrafine particle injection material composition of the present invention, the content of the cement clinker is in the range of 2 to 25% by mass in 100% by mass of the ultrafine particle cement. For example, even if it is a cement clinker with a C3A content of 5% by mass or less, the C3A content in the ultrafine particle cement increases as the cement clinker content increases. For this purpose, it is effective to limit the content of the cement clinker and reduce the C3A content in the ultrafine particle cement as much as possible. By setting the content to 25% by mass or less, the ultrafine particle injection material composition exhibits more sufficiently excellent injection properties without increasing aggregated particles as the C3A content in the ultrafine particle cement increases. be able to. Moreover, when content of a cement clinker is less than 2 mass%, there exists a possibility that intensity | strength expression may be scarce and it may not be useful practically. The content of cement clinker is more preferably 5 to 25% by mass. More preferably, it is 5-20 mass%.

In the ultrafine particle injection material composition of the present invention, the content of the blast furnace slag is 74 to 97 mass% with respect to 100 mass% of the ultrafine particle cement. By setting it as 74 mass% or more, the effect of relaxing the hydration activity of the cement clinker becomes sufficient, and the excellent injectability of the ultra-fine particle injection material composition can be exhibited. On the other hand, if it exceeds 97% by mass, strength development is not sufficient from the beginning, which may be impractical. In order to fully express the effects of the present invention, the content of blast furnace slag is more preferably 74 to 95% by mass. More preferably, it is 77-92 mass%.

In the ultra-fine particle injection material composition of the present invention, the blast furnace slag is not particularly limited, but one or two of slow-cooled slag and granulated slag can be suitably used. More preferred is granulated slag from the standpoint of strength development. If ultra-fine particle cement containing cement clinker and gypsum is used without using blast furnace slag, hydration activity is high when kneaded with water and agglomeration may occur, which may cause apparent particle coarsening. is there. By using blast furnace slag, the hydration activity when kneaded with water can be relaxed, and in the ultra-fine particle injection material composition, aggregated particles can be reduced, and dispersion retention can be excellent. Medium to long-term strength and durability can be improved.

In the ultrafine particle injection material composition of the present invention, the content of the gypsum is in the range of 1 to 5 mass% with respect to 100 mass% of the ultrafine particle cement. If the amount is less than 1% by mass, the initial strength expression decreases, and if it exceeds 5% by mass, the amount of ettringite produced by reaction with C3A increases, and high injectability cannot be obtained. There are many layers, and there is a possibility that a uniform ground improvement effect cannot be obtained. More preferably, it is 1-4 mass% as content of gypsum. More preferably, it is 2-4 mass%.

In the ultrafine particle injection material composition of the present invention, the gypsum is not particularly limited, but dihydrate gypsum, hemihydrate gypsum, type II anhydrous gypsum, type III anhydrous gypsum, and the like are preferable. These may be chemical gypsum, natural products, or heat-treated. From the viewpoint of injectability and strength development, type II anhydrous gypsum is preferable.

By using the above-mentioned gypsum as a constituent component, it is possible to obtain an initial strength development property and a medium to long-term hydration promoting effect of blast furnace slag. On the other hand, gypsum is an easily pulverizable material, and is easily segregated by mixing and pulverization, like C3A. Depending on the type of gypsum, it is active. For example, hemihydrate gypsum hardens in a very short time by hydration. The gypsum that reacts rapidly with C3A is preferably not more than a specific amount so that the ultra-fine particle injection material composition can exhibit excellent injectability. In addition, gypsum has a lower density than other materials and causes material separation during pressure injection. Therefore, when added in large quantities, gypsum has poor adhesion when an ultra-fine particle injection material composition is used as the injection material. There is a risk of forming a gypsum layer.
Although content of the said ultra-fine particle cement is not specifically limited, 95-99.7 mass% in conversion of solid content is preferable with respect to 100 mass% of ultra-ultra fine particle injection material compositions. If it is less than 95% by mass, the economical efficiency is deteriorated and the cost may not be suitable. If it exceeds 99.7% by mass, the dispersibility and dispersion retention of the ultrafine particle injection material composition may not be sufficiently exhibited. More preferably, it is 96-99.5 mass%. More preferably, it is 97-99 mass%.

The polycarboxylic acid-based dispersant used in the present invention is not particularly limited as long as it exhibits the effects of the present invention. For example, a dispersant used in the cement / concrete field or a commercially available water reducing agent for cement / concrete is preferable. . Among commercially available cement / concrete water reducing agents, a dispersant that can be suitably used in the present invention is called a polycarboxylic acid-based cement dispersant or water reducing agent, and can be an essential component of a cement dispersant. It contains a polycarboxylic acid copolymer. Such a polycarboxylic acid-based cement dispersant is known as a dispersant capable of obtaining high dispersibility and high dispersion retention in a small amount due to steric hindrance. In the polycarboxylic acid-based cement dispersant, the polycarboxylic acid-based copolymer may be any one having a free carboxyl group and capable of exhibiting water reduction performance with respect to the cement composition. More than one species can be used, but a polycarboxylic acid copolymer having a polyalkylene glycol in the side chain is preferred. In the case where polyalkylene glycol is contained in the side chain, it is known that the dispersibility and dispersion retainability vary depending on the main chain length, the side chain length, the amount of carboxylic acid, and the like.

The polycarboxylic acid-based cement dispersant used in the cement / concrete field can be suitably used in the ultra-fine particle injection material composition of the present invention. Compared to, it can exhibit high dispersibility and high dispersibility.
The polycarboxylic acid-based copolymer contained in the polycarboxylic acid-based dispersant of the present invention has a free carboxyl group as in the above-mentioned cement dispersant, and exhibits dispersion performance in ultra-fine particle cement. The injection material composition only needs to have excellent dispersibility (permeability) and dispersion retention, and one or two or more kinds can be used, but polyalkylene glycol is used in the side chain. It is preferable to have. That is, the polycarboxylic acid dispersant preferably has a repeating unit derived from an unsaturated polyalkylene glycol monomer and a repeating unit derived from an unsaturated carboxylic acid monomer. Thus, the polycarboxylic acid dispersant is a polycarboxylic acid copolymer having a repeating unit derived from an unsaturated polyalkylene glycol monomer and a repeating unit derived from an unsaturated carboxylic acid monomer. An ultra-fine particle injection material composition containing a coalescence is also one of the preferred embodiments of the present invention.

The polycarboxylic acid copolymer preferably has a long side chain. By using a copolymer having a long side chain, the ultra-fine particle injection material composition containing such a polycarboxylic acid-based dispersant is excellent in dispersibility (penetration) and dispersion retention. The side chain length, dispersibility (permeability), and dispersion retention will be conceptually explained. When the side chain is long, steric hindrance is likely to occur, so the ultrafine particles adsorbed with the polycarboxylic acid copolymer The cement particles are less likely to approach each other and can be excellent in dispersibility. In addition, when a specific ultra-fine cement particle is adsorbed on the surface, the polycarboxylic acid copolymers are difficult to approach each other due to steric hindrance. It will be avoided that the cover is excessive. For this reason, it is possible to sufficiently secure a portion where the ultra-fine particle cement particles are brought into contact with water, whereby hydration is promoted, the solution is condensed in a short time, and the setting time can be shortened.

On the other hand, when the side chain is short, steric hindrance is unlikely to occur, so the polycarboxylic acid-based copolymer covers the ultra-fine particle cement particles, which prevents the ultra-fine particle cement particles from being hydrated and may require a long time for setting. There is. Thus, since the polycarboxylic acid copolymer contained in the polycarboxylic acid-based dispersant is excellent in dispersibility and dispersion retention, the side chain is preferably long. The polycarboxylic acid copolymer will be described later.

The addition amount of the polycarboxylic acid-based dispersant is not particularly limited, but is preferably 0.3 to 5.0% by mass in terms of solid content with respect to 100% by mass of the ultrafine particle cement. If the amount is less than 0.3% by mass, the dispersibility and dispersion retention of the ultra-fine particle injection material composition may not be sufficiently exhibited. If the amount exceeds 5.0% by mass, the amount added will be excessively increased. There is a risk that it will not be suitable in terms of cost. More preferably, it is 0.5-4.0 mass%. More preferably, it is 1.0-3.0 mass%.

As the ultra-fine particle injection material composition, an ultra-fine particle cement and a polycarboxylic acid-based dispersant are mixed as essential components. As described above, usually, the ultra-fine particle injection material composition contains water. is there. Such water is not particularly limited as long as the effects of the present invention are exhibited, but water defined in Appendix 9 of JIS A 5308 is preferable. Such water defined in Annex 9 of JIS A 5308 does not adversely affect the performance of concrete, and water other than water supply and water supply (river water, lake water, well water, ground water, etc.) is specified. When water other than these, for example, a strong electrolyte such as seawater, is used, aggregation of cement particles is promoted, and high injectability may not be obtained.

The content of the water is not particularly limited as long as the effects of the present invention are exhibited, and can be appropriately set according to the constituent components and use of the ultra-fine particle injection material composition (ultra-ultra fine particle cement slurry). For example, when used as an injection material, the water / ultrafine particle cement mass ratio is preferably 80 to 10,000% when the slurry is poured into the ground or the like. If it is less than 80%, the concentration of the ultra-fine particle cement slurry is too high, and a high pressure may be required for injection. If it exceeds 10,000%, the concentration of the slurry is too low and sufficient strength is not exhibited. There is a fear. More preferably, it is 90-5000%, More preferably, it is 100-2000%. The content of the ultra-fine particle cement when the slurry is injected into the ground or the like is 0.9 to 56% by mass when the ultra-fine particle injection material composition (ultra-ultra fine particle cement slurry) is 100% by mass. It is preferable that If the amount is less than 0.9% by mass, the concentration of the ultra-fine particle cement slurry may be too low and sufficient strength may not be exhibited. If the amount exceeds 56% by mass, the concentration of the slurry is too high for injection. High pressure may be required. More preferably, it is 1.9-53 mass%, More preferably, it is 4-50 mass%.

In addition to the above, the ultra-fine particle injection material composition of the present invention has a cement dispersant other than polycarboxylic acid, AE agent, antifoaming agent, and curing (condensation) as long as the effects of the present invention are exhibited. Retarder, hardening (coagulation) accelerator, cement wetting agent, swelling agent, waterproofing agent, quick setting agent, thickener, flocculant, fast hardener, shrinkage reducing agent, separation reducing agent, neutralization inhibitor, prevention Other concrete admixtures such as rusting agents, other water-soluble polymer compounds, pozzolanic materials, clay minerals, foaming agents, foaming agents, antifreeze agents, etc. can be used, cement and concrete Admixtures and admixtures known in the art may be used in combination.

Specific examples of cement dispersants other than the above-mentioned polycarboxylic acid series include polyalkylaryl sulfonate series such as naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene sulfonic acid formaldehyde condensate, anthracene sulfonic acid formaldehyde condensate; melamine sulfonic acid Melamine formalin sulfonates such as formaldehyde condensates; aromatic amino sulfonates such as aminoaryl sulfonic acid-phenol-formaldehyde condensates; lignin sulfonates such as lignin sulfonate and modified lignin sulfonate And various sulfonic acid cement dispersants such as polystyrene sulfonate salt.

Specific examples of the AE agent include sodium hydroxystearate, lauryl sulfate, ABS (alkyl benzene sulfonic acid), LAS (linear alkyl benzene sulfonic acid), alkane sulfonate, polyoxyethylene alkyl (phenyl) ether, polyoxyethylene alkyl ( Phenyl) ether sulfate or a salt thereof, polyoxyethylene alkyl (phenyl) ether phosphate or a salt thereof, protein material, alkenylsulfosuccinic acid, α-olefin sulfonate, and the like.

In the ultrafine particle injection material composition of the present invention, an alkyl ether type anionic surfactant type, a modified rosin acid compound type anionic surfactant type, an alkyl sulfonic acid compound type anionic surfactant type, a high Various AE agents such as alkylcarboxylate type anionic surfactant type, modified alkylcarboxylic acid compound type anionic surfactant type, Vinsol (trade name, manufactured by Yamasoh Chemical Co., Ltd.) or micro-air (Micro- Air, trade name, manufactured by Master Builders) may be used in combination.

Specific examples of the antifoaming agent include polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene Polyoxyalkylene alkyl ethers such as polyoxypropylene 2-ethylhexyl ether and oxyethyleneoxypropylene adducts of higher alcohols having 12 to 14 carbon atoms; polyoxyalkylene alkyl ethers such as polyoxypropylene phenyl ether and polyoxyethylene nonylphenyl ether Alkylene (alkyl) aryl ethers; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3-methyl- 1 Acetylene ethers obtained by addition polymerization of alkylene oxide to acetylene alcohol such as butyn-3-ol; (poly) oxyalkylene fatty acid esters such as diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate; polyoxyethylene Polyoxyalkylene sorbitan fatty acid esters such as sorbitan monolaurate and polyoxyethylene sorbitan trioleate; polyoxyalkylene alkyl (aryl) ether sulfate such as sodium polyoxypropylene methyl ether sulfate and sodium polyoxyethylene dodecylphenyl ether sulfate Ester salts; polyoxyalkylenes such as polyoxyethylene stearyl phosphates Kill phosphoric acid esters; polyoxypropylene polyoxyethylene laurylamine (1-20 mol addition of propylene oxide, 1-20 mol addition product of ethylene oxide, etc.), cured beef tallow amine added with alkylene oxide (1-20 mol addition of propylene oxide, Polyoxyalkylene alkylamines such as ethylene oxide 1-20 mol adducts, etc .; polyoxyalkylene amides, etc. These antifoaming agents may use only 1 type and may use 2 or more types together. The antifoaming agent may be added before polymerization is started, during polymerization, or after polymerization. Moreover, it is preferable that an addition rate shall be 0.0001-10 mass% with respect to the total mass of the polymer for ultra-fine particle injection material compositions. That is, it is 0.0001-10 mass% with respect to a polycarboxylic acid type dispersing agent, and can be added to the dispersing agent in advance.

Specific examples of the antifoaming agent other than the oxyalkylene type include mineral oil type antifoaming agents such as coconut oil and liquid paraffin; fat and oil type antifoaming agents such as animal and vegetable oils, sesame oil, castor oil, and adducts thereof with these alkylene oxides; oleic acid , Stearic acid, fatty acid-based antifoaming agents such as these alkylene oxide adducts; fatty acid ester-based antifoaming agents such as glycerin monoricinoleate, alkenyl succinic acid derivatives, sorbitol monolaurate, sorbitol trioleate, natural wax; octyl alcohol , Hexadecyl alcohol, acetylene alcohol, glycols, etc .; defoamers such as acrylate polyamines; phosphate defoamers such as tributyl phosphate, sodium octyl phosphate; aluminum stearate , Calcium oleate, etc. Genus soap antifoaming agents; dimethylsilicone oils, silicone pastes, silicone emulsions, organic modified polysiloxanes (polyorganosiloxanes dimethylpolysiloxane), silicone-based defoaming agent such as fluorosilicone oil, and the like.

Specific examples of the curing accelerator include soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide and calcium iodide; chlorides such as iron chloride and magnesium chloride; sulfates; potassium hydroxide; Sodium hydroxide; carbonate; thiosulfate; formate such as formic acid and calcium formate; alkanolamine; alumina cement; calcium aluminate silicate.

Specific examples of the water-soluble polymer compound include nonionic cellulose ethers such as methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxyethylcellulose, hydroxypropylcellulose; methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose. Hydrophobic substituents in which part or all of the hydroxyl groups of the alkylated or hydroxyalkylated derivatives of polysaccharides have a hydrocarbon chain having 8 to 40 carbon atoms as a partial structure, and sulfonic acid groups or the like Derivatives of polysaccharides substituted with ionic hydrophilic substituents having a partial structure thereof: yeast glucan, xanthan gum, β-1,3 glucans (straight and branched chain) For example, polysaccharides produced by microbial fermentation such as curdlan, paramylon, pachyman, scleroglucan, laminaran, etc.); polyacrylamide; polyvinyl alcohol; starch; starch phosphate ester; sodium alginate; Gelatin; a copolymer of acrylic acid having an amino group in the molecule and a quaternary compound thereof.

In the ultrafine particle injection material composition of the present invention, (a) 2-25% by mass of cement clinker having a content of 3CaO.Al ₂ O ₃ of 5% by mass or less, (b) 74-97% by mass of blast furnace slag, (C) Highly fine powder containing 1 to 5% by mass of gypsum, ultra-fine particle cement having a particle size of 1 to 5 μm in the powder and 60 to 80% by volume, polycarboxylic acid-based dispersion A slurry comprising an agent and water is also one of the preferred forms of the present invention. Thus, by specifying the blending ratio of cement clinker, blast furnace slag and gypsum with reduced C3A, which is a mineral with high hydration activity, and containing a polycarboxylic acid-based dispersant and water, Even if ultrafine particles exceeding the particle size are made, aggregation of particles in the slurry can be reduced as much as possible, and high injectability exceeding conventional ultrafine particle cement can be obtained.

The present invention is also a method for producing the ultra-fine particle injection material composition of the present invention described above, wherein the production method includes a high-speed stirring step of mixing and stirring at a peripheral speed of 314 m / min or more. It is also a method for producing a composition. Having a high-speed stirring step of mixing and stirring at 2500 rpm or higher is also a preferred form of the method for producing the ultrafine particle injection material composition of the present invention. In the said manufacturing method, the ultra-fine particle injection material composition suitable for various uses, such as an injection material, can be manufactured by having the said high-speed stirring process.
Further, as a preferred embodiment of the method for producing the ultra-fine particle injection material composition of the present invention, an ultra-fine particle injection material composition obtained by mixing an ultra-ultra fine particle cement, a polycarboxylic acid-based dispersant and water as essential components is used. The manufacturing method includes a form having a high-speed stirring step of mixing and stirring at a peripheral speed of 314 m / min or more. A form having a high-speed stirring step of mixing and stirring at 2500 rpm or higher is also a preferable form.
The peripheral speed means the tip peripheral speed of the stirring blade.
The peripheral speed is the following formula:
Peripheral speed (m / min) = blade diameter (m) × π × stirring shaft speed (rpm)
It can ask for.
In addition, in the said manufacturing method, it is preferable to use what was mentioned above as a component (ultra ultrafine particle cement, a polycarboxylic acid type dispersing agent, water, etc.) contained in an ultrafine particle injection material composition. Hereinafter, the method for producing an ultrafine particle injection material composition having a high-speed stirring step is also referred to as a high-speed stirring method.

In the present invention, by stirring at a high speed under the above conditions, the shearing action due to the high-speed rotation of the mixer sufficiently disaggregates the agglomerated primary and secondary particles of the ultra-fine cement, and the dispersant quickly appears on the newly appearing particle surface. By adsorbing, an ultra-fine particle injection material composition having high dispersibility and high dispersion retention can be obtained. On the other hand, when ultra-fine particle cement, polycarboxylic acid-based dispersant and water are mixed by a normal production method, the particle aggregation rate often exceeds the adsorption rate of the dispersant. There is a possibility that an ultra-fine particle injection material composition (ultra-fine particle cement-type slurry for grout) having good properties and dispersion retention cannot be obtained. For example, depending on the manufacturing method, the obtained slurry may be inferior to conventional ultrafine cement.

If the peripheral speed is less than 314 m / min in the high-speed stirring step, dispersion of the ultra-fine particle cement particles becomes insufficient, and the injectability of the ultra-fine particle injection material composition may be lowered. There is a similar possibility even if it is less than 2500 rpm. More preferably, the peripheral speed is 376.8 m / min or more. 3000 rpm or more is also preferable. The upper limit of the stirring speed in the high-speed stirring step is not particularly limited, but practically, the peripheral speed is preferably 1884 m / min or less. 12000 rpm or less is also preferable. Even if it exceeds the peripheral speed of 1884 m / min, a remarkable improvement effect is not seen in the injection property, and there is a risk that the cost is increased in terms of equipment. There is a similar risk even if the speed exceeds 12000 rpm. More preferably, the peripheral speed is 1570 m / min or less. 10,000 rpm or less is also preferable. The range is preferably a peripheral speed of 314 to 1884 m / min. Also preferred is 2500-12000 rpm. In the high-speed stirring step, the mixing and stirring speed can be set according to the rotation speed of the stirring shaft of the high-speed mixer.

Although it does not specifically limit as a high-speed mixer used at the said high-speed stirring process, The high-speed mixer which has a stirring shaft and a stirring blade is preferable. Specifically, one kind of multi-purpose digital stirrer (manufactured by Iuchi Seieido Co., Ltd., stirring shaft maximum rotation speed 5000 rpm, stirring blade diameter 40 mm), blender (Oster Corporation, stirring shaft maximum rotation speed 15700 rpm, stirring blade diameter 50 mm), etc. Or 2 or more types can be used. In addition, the above-described high-speed mixer is a mixer for test use suitable for a small amount of stirring. When the ultra-fine particle injection material composition is used by being injected into, for example, the ground or rock, it is appropriate depending on the scale to be used. A high speed mixer can be used.
The stirring time in the high-speed stirring step can be appropriately set according to various conditions such as the use of the ultra-fine particle injection material composition to be produced, the type and amount of raw materials, the mixer to be used, and the temperature during stirring. For example, when an ultra-fine particle injection material composition is used as an injection material, and the raw material is a high-fine powder containing cement clinker, blast furnace slag and gypsum, and ultra-fine particle cement is used, the mixture is stirred for 1 to 10 minutes. Is preferred.

The high-speed stirring step is a method for producing a super-ultrafine particle injection material composition that requires ultra-fine particle cement, a polycarboxylic acid-based dispersant, and water, but it is preferable to stir at the above stirring speed. These components only need to be present when stirring at a high speed with the above stirring speed, and the order of addition and addition method are not particularly limited, but (1) when using a liquid dispersant, A form in which cement is added to (water + dispersant) is preferable. In the case of using a powder dispersant, (2) a form in which cement is added to a solution in which the dispersant powder is added to water, and (3) a form in which water is added to the mixture of the cement and the dispersant are preferable. As described above, the polycarboxylic acid-based dispersant can be used as either a liquid or a powder, and can be appropriately selected according to various conditions.
As the addition / mixing form of the above components, the above-described form (1) is preferable because a uniform slurry can be easily obtained without agglomeration.

The present invention further relates to a method for producing the ultra-fine particle injection material composition of the present invention described above, wherein the production method comprises mixing and stirring with ultra-fine particle cement and water as essential components, followed by further adding water and re-stirring It is also a manufacturing method of the ultra-fine particle injection material composition which has the process to do.
In the production method described above, ultra-fine cement and water as essential components are mixed and stirred (hereinafter also referred to as an initial hydration stirring step), and then further added and re-stirred (hereinafter also referred to as a second hydration stirring step). However, as the number of times of adding water and the number of times of stirring the mixture, it is preferable that the number of times of water addition and stirring in the initial water stirring step and the second water stirring step is at least 2 times or more, respectively. Thus, by adding water and stirring twice or more, the concentration of the ultra-fine particle injecting material composition can be easily adjusted, and a slurry having high dispersibility and high dispersibility can be obtained. In addition, in the said manufacturing method, it is preferable to use what was mentioned above as a component (ultra ultrafine particle cement, a polycarboxylic acid type dispersing agent, water, etc.) contained in an ultrafine particle injection material composition.

The number of hydration and stirring is not particularly limited as long as it is twice or more. When the number of hydration and the number of stirring is 2 times or more, the number of hydration and the number of stirring may be different from each other, as long as they have an initial hydration stirring step and a second hydration stirring step. The method of producing the ultra-fine particle injection material composition in which the hydration and stirring are performed twice or more is also referred to as “two-stage hydration stirring method”. The number of times of hydration and stirring is preferably two because the process becomes complicated when the number of hydration and stirring is increased.

Hereinafter, the initial water stirring step and the second water stirring step will be described. In addition, when the hydration exceeds twice, the initial hydration step and the hydration other than the second hydration step (also referred to as other hydration) are not particularly limited as long as hydration is performed before the second hydration step. . In the other hydration, the amount of each hydration is not particularly limited as long as it becomes the water / ultrafine particle cement mass ratio described later in the second hydration stirring step. Moreover, when stirring exceeds twice, it may be stirred at any stage, before the initial water stirring step, between the initial water stirring step and the second water stirring step, or after the second water stirring step. It can stir and may be stirred continuously.

The amount of water added in the initial hydration stirring step and the second hydration stirring step is set to be smaller than a predetermined water / ultrafine particle cement mass ratio in the initial hydration stirring step. It is preferable to be a fine particle cement mass ratio. In the above-mentioned two-stage water agitation method, since the adsorption of the dispersant to the cement particles is a liquid layer adsorption, the initial water / ultrafine particle cement mass ratio is reduced, so that the surface of the cement particles can be rapidly hydrated. A film can be formed. Also, by reducing the mass ratio of water / ultrafine particle cement, the concentration of the dispersant in the liquid can be kept high, and the adsorption rate to the particles can be increased to form a uniform adsorption layer on the particle surface. it can. Moreover, in the second hydration stirring step, the slurry re-stirred after hydration to a water / ultrafine particle cement mass ratio described later has high dispersibility and high dispersion retention, and can be suitably used for grout.

The water / ultrafine particle cement mass ratio is preferably 30 to 90% in the initial water stirring step (at the time of initial stirring). If it is less than 30%, there is a possibility that the amount of water is small and uniform mixing and stirring cannot be performed. On the other hand, if it exceeds 90%, the initial amount of dispersant adsorbed is small, and there is a possibility that the dispersion effect by the two-stage water stirring method cannot be obtained. More preferably, it is 40 to 70%.

The water / ultrafine particle cement mass ratio in the second hydration stirring step is preferably in the range described in the water / ultrafine particle cement mass ratio of the ultrafine particle injection material composition, and is 100 to 10,000%. It is preferable to do. By setting it as the said range, the obtained ultra-fine particle injection material composition can be used for an injection | pouring use as it is. Thus, in the two-stage water stirring method of the present invention, in the initial water stirring step, a small amount of water is added and stirred, and in the second water stirring step, the water / ultrafine particle cement mass ratio is in the above range, A water / ultrafine particle cement mass ratio suitable for pouring into the ground or the like is obtained, and a uniform slurry is obtained by stirring, which can be suitably used as an injecting material.

The stirring speed of the two-stage water stirring method is not particularly limited, but the peripheral speed is preferably 37.7 m / min or more in the initial water stirring step and the second water stirring step. 300 rpm or more is also preferable. When the peripheral speed is less than 37.7 m / min, the stirring is not sufficient and there is a possibility that a uniform slurry is not obtained. There is a similar possibility even if it is less than 300 rpm. More preferably, the peripheral speed is 75.4 m / min or more, and further preferably the peripheral speed is 125.6 m / min or more. 600 rpm or more is also more preferred, and 1000 rpm or more is even more preferred. The upper limit of the stirring speed is not particularly limited. In addition, when stirring is performed more than twice, it is suitable as it is as above about stirring speeds other than an initial stage water stirring process and a 2nd water stirring process.

The above-mentioned two-stage water stirring method is not particularly limited as long as it has a step of mixing and stirring with ultra-fine particle cement and water as essential components, further adding water and re-stirring, and the above ultra-fine particle injection material composition The polycarboxylic acid-based dispersant contained as an essential component may be added at any stage. In order to obtain a uniform slurry without agglomerating the ultra-fine particle cement, the polycarboxylic acid-based dispersant is preferably in a form in which the polycarboxylic acid-based dispersant is included in the initial water stirring step. The mixing form of such a polycarboxylic acid-based dispersant is preferably the same as that described as the method for adding the ultra-fine particle cement, the polycarboxylic acid-based dispersant and water in the high-speed stirring step. . That is, the above forms (1) to (3) ((1) a form in which cement is put into a dispersant solution (water + dispersant), (2) a form in which cement is put into a solution in which a dispersant powder is added to water, ( 3) Form in which water is added to a mixture of cement and dispersant), and (1) When using a liquid dispersant, a form in which cement is added to a dispersant solution (water + dispersant) is preferred.

As described above, the two-stage water stirring method is preferably mixed and stirred at a water / ultrafine particle cement mass ratio of 30 to 70% during initial stirring. It is preferable to mix and stir at a cement mass ratio of 100 to 10000%. As described above, the mixing and stirring method is a two-stage water stirring method in which the water ultra-fine particle cement mass ratio at the initial stirring is 30 to 70%, and then mixed and stirred to a predetermined water / ultra-fine particle cement mass ratio and then re-stirred. The ultra-fine cement cement grout slurry, which is a method, is also one of the preferred embodiments of the present invention.

The high-speed stirring method and the two-stage water stirring method of the present invention can be used independently, but it is preferable to use the high-speed stirring method and the two-stage water stirring method in combination. By using these in combination, it is possible to produce an ultra-fine particle injection material composition having high dispersibility and high dispersibility. The combined use method is not particularly limited as long as it includes a high-speed stirring step of mixing and stirring at a peripheral speed of 314 m / min or more and a step of mixing and stirring with ultra-fine particle cement and water as essential components, followed by further adding water and stirring again. In at least one of the initial water stirring step and the second water stirring step of the step water stirring method, a high speed stirring step of mixing and stirring at a peripheral speed of 314 m / min or more is preferable. In addition, the combined method preferably includes a high-speed stirring step of mixing and stirring at 2500 rpm or more and a step of mixing and stirring with ultrafine cement and water as essential components, followed by further adding water and re-stirring. In at least one of the initial hydration stirring step and the second hydration stirring step, a high-speed stirring step of mixing and stirring at 2500 rpm or more is more preferable. More preferably, high-speed stirring is performed in the initial water stirring step, and still more preferably high-speed stirring is performed in both the initial water stirring step and the second water stirring step.

The high-speed stirring method and / or the two-stage water stirring method can also be applied as a stirring method of a grout slurry using a conventional ultrafine particle cement, can reduce the number of aggregated particles produced, and has excellent injectability. An ultrafine particle injection material composition can be obtained.

Below, the polycarboxylic acid-type copolymer contained in the polycarboxylic acid-type dispersing agent of this invention is explained in full detail.
The polycarboxylic acid-based copolymer is not particularly limited as long as it can exhibit dispersion performance and dispersion retention performance with respect to the particles contained in the ultra-fine particle injection material composition. It is preferable to use a polycarboxylic acid copolymer having an alkylene glycol. Such a polycarboxylic acid-based copolymer can be an essential component of the ultra-fine particle injection material composition.

The polycarboxylic acid copolymer having a polyalkylene glycol in the side chain has a repeating unit derived from an unsaturated polyalkylene glycol monomer and a repeating unit derived from an unsaturated carboxylic acid monomer. It is preferable.
As said polycarboxylic acid-type copolymer, following General formula (1);

(In the formula, R ¹ and R ² are the same or different and represent a hydrogen atom or a methyl group. R ³ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. The average addition mole number of an oxyalkylene group is a number from 2 to 300. R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.) Unit (I) and the following general formula (2);

(Wherein R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or a methyl group. M ¹ represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group). The polycarboxylic acid copolymer (P-1) having the carboxylic acid structural unit (II) represented is preferable. Moreover, as said polycarboxylic acid-type copolymer, following General formula (3);

(In formula, R < ⁷ >, R < ⁸ > and R < ⁹ > are the same or different and represent a hydrogen atom or a methyl group. R < ¹⁰ > represents a C1-C5 hydrocarbon group. R < ¹¹ > O is the same. Or, differently, it represents an oxyalkylene group having 2 to 18 carbon atoms, b represents an average number of added moles of the oxyalkylene group, and is a number of 2 to 300. R ¹² is a hydrogen atom or 1 carbon atom. A polyoxyalkylene ether structural unit (III) represented by the following general formula (4);

(In the formula, R ¹³ and R ¹⁴ are the same or different and each represents a hydrogen atom, a methyl group or —COOM ^3. However, R ¹³ and R ¹⁴ do not simultaneously represent —COOM ^3. R ¹⁵ represents hydrogen. Represents an atom, a methyl group or —CH ₂ COOM ^{4. When} R ¹⁵ is —CH ₂ COOM ⁴ , R ¹³ and R ¹⁴ are the same or different and represent a hydrogen atom or a methyl group, M ² , M ³ and M ⁴ represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group or an organic amine group.) A polycarboxylic acid copolymer (P-2) having a carboxylic acid structural unit (IV) represented by Is preferred.

That is, the polycarboxylic acid-based dispersant preferably includes the polycarboxylic acid-based copolymer (P-1) and / or the polycarboxylic acid-based copolymer (P-2). Such a polycarboxylic acid-based dispersant may be composed of only the above-mentioned polycarboxylic acid-based copolymer, and may contain others, but the polycarboxylic acid-based copolymer is a main component. It is preferable to do. The polycarboxylic acid copolymers (P-1) and (P-2) have the above essential structural units (repeating units) and are derived from the monomer (e) described later. It may further have (V). Each of these structural units may be one kind or two or more kinds.

The polycarboxylic acid copolymer (P-1) is composed of a monomer that gives the structural unit (I) (for example, the monomer (a) described later) and a monomer that gives the structural unit (II) (for example, The monomer component containing the monomer (b)) described below as an essential component can be copolymerized and produced. Such a monomer component may further contain a monomer that gives the structural unit (V) (for example, a monomer (e) described later). In addition, when each structural unit is 1 type, it is sufficient to use one type of monomer that provides each structural unit. When there are 2 or more types of structural units, a single amount that provides each structural unit. What is necessary is just to use 2 or more types of bodies, respectively.

The ratio of each structural unit constituting the polycarboxylic acid copolymer (P-1) is, by mass ratio, structural unit (I) / structural unit (II) / structural unit (V) = 1 to 99 /. It is preferable that it is 99-1 / 0-50. More preferably, the structural unit (I) / the structural unit (II) / the structural unit (V) = 50 to 99/50 to 1/0 to 49, and more preferably the structural unit (I) / the structural unit (II) / the structural unit. (V) = 60 to 95/40 to 5/0 to 30, most preferably the structural unit (I) / the structural unit (II) / the structural unit (V) = 65 to 90/35 to 10/0 to 10. . However, the total of the structural unit (I), the structural unit (II) and the structural unit (V) is 100% by mass.

The polycarboxylic acid copolymer (P-1) is a polymerized monomer component containing a monomer (for example, monomer (b) described later) as an essential component to give the structural unit (II). Alternatively, it may be produced by directly esterifying an alkoxypolyalkylene glycol with respect to at least a part of the carboxyl groups of the polymer obtained. In the general formula (1), examples of the hydrocarbon group having 1 to 30 carbon atoms in R ⁴ include an alkyl group having 1 to 30 carbon atoms, a phenyl group having 6 to 30 carbon atoms, an alkylphenyl group, Examples thereof include an aromatic group having a benzene ring such as a phenylalkyl group, a phenyl group substituted with a (alkyl) phenyl group, and a naphthyl group, and an alkenyl group having 2 to 30 carbon atoms. Moreover, although the average added mole number a of an oxyalkylene group is a number of 2-300, the number of 5-300 is preferable. More preferably, the number is 10 to 250, still more preferably 20 to 200, and most preferably 50 to 100. Further, the number of carbon atoms of R ⁴ is preferably 1 to 22. More preferably, it is 1-18, More preferably, it is 1-12, Especially preferably, it is 1-6, More preferably, it is 1-5, Most preferably, it is 1-3.

As the number of carbon atoms of the oxyalkylene group R ³ O in the general formula (1), 2 to 18 is appropriate, but 2 to 8 is preferable. More preferably, it is 2-4. Moreover, when it becomes one type as the structural unit (I), it is preferable to have an oxyethylene group as an essential component in the oxyalkylene group in order to ensure a balance between hydrophilicity and hydrophobicity, and more preferably 50 mol% or more. Particularly preferably, 60 mol% or more is an oxyethylene group. On the other hand, when there are two or more types of structural units (I), it is preferable to have an oxyethylene group as an essential component in the oxyalkylene group of any one of the structural units (I).

Examples of the monomer (a) giving the structural unit (I) include addition of an alkylene oxide having 2 to 18 carbon atoms to a dehydrogenation (oxidation) reaction product of (meth) acrylic acid, crotonic acid or fatty acid. Or carbon atoms such as methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, etc. C1-C30 saturated aliphatic alcohols, allyl alcohol, methallyl alcohol, crotyl alcohol, oleyl alcohol, etc., C3-C30 unsaturated aliphatic alcohols, cyclohexanol, etc. C3-C30 Alicyclic alcohols, phenol, phenylmethanol (benzyl Any of aromatic alcohols having 6 to 30 carbon atoms such as (rucol), methylphenol (cresol), p-ethylphenol, dimethylphenol (xylenol), pt-butylphenol, nonylphenol, dodecylphenol, phenylphenol, naphthol, etc. Examples include an ester compound of an alkoxypolyalkylene glycol obtained by adding an alkylene oxide having 2 to 18 carbon atoms and (meth) acrylic acid or crotonic acid. In general formula (1), An ester compound of an alkoxypolyalkylene glycol and (meth) acrylic acid or crotonic acid corresponding to the case where R ⁴ is a hydrocarbon group is preferred.

Specific examples of the chemical name of the monomer (a) include the following. Methoxy polyethylene glycol mono (meth) acrylate, ethoxy polyethylene glycol mono (meth) acrylate, 1-propoxy polyethylene glycol mono (meth) acrylate, 2-propoxy polyethylene glycol mono (meth) acrylate, 1-butoxy polyethylene glycol mono (meth) acrylate 2-butoxypolyethylene glycol mono (meth) acrylate, 2-methyl-1-propoxypolyethylene glycol mono (meth) acrylate, 2-methyl-2-propoxypolyethylene glycol mono (meth) acrylate, 1-pentyloxypolyethylene glycol mono ( (Meth) acrylate, 1-hexyloxypolyethylene glycol mono (meth) acrylate, cyclohexyloxypolyethylene Glycol mono (meth) acrylate, 1-octyloxypolyethylene glycol mono (meth) acrylate, 2-ethyl-1-hexyloxypolyethylene glycol mono (meth) acrylate, nonylalkoxypolyethyleneglycol mono (meth) acrylate, laurylalkoxypolyethyleneglycolmono (Meth) acrylate, cetylalkoxypolyethyleneglycol mono (meth) acrylate, stearylalkoxypolyethyleneglycolmono (meth) acrylate, phenoxypolyethyleneglycolmono (meth) acrylate, phenylmethoxypolyethyleneglycolmono (meth) acrylate, methylphenoxypolyethyleneglycolmono ( (Meth) acrylate, p-ethylphenoxypolyethyleneglycol Mono (meth) acrylate, dimethylphenoxypolyethylene glycol mono (meth) acrylate, pt-butylphenoxypolyethylene glycol mono (meth) acrylate, nonylphenoxypolyethylene glycol mono (meth) acrylate, dodecylphenoxypolyethylene glycol mono (meth) acrylate, Phenylphenoxypolyethylene glycol mono (meth) acrylate, naphthoxypolyethylene glycol mono (meth) acrylate, esterified product of (meth) allyl alcohol and (meth) acrylic acid to which ethylene oxide is added, crotyl alcohol to which ethylene oxide is added Various alkoxy polyethylene glycol mono (meth) acrylates such as esterified products with (meth) acrylic acid.

Methoxy polypropylene glycol mono (meth) acrylate, ethoxy polypropylene glycol mono (meth) acrylate, 1-propoxy polypropylene glycol mono (meth) acrylate, 2-propoxy polypropylene glycol mono (meth) acrylate, 1-butoxy polypropylene glycol mono (meth) acrylate , Various types of alkoxypolypropylene glycol mono ((ester) of (meth) allyl alcohol and propylene oxide and (meth) acrylic acid, ester of crotyl alcohol and propylene oxide and (meth) acrylic acid) (Meth) acrylates.

Methoxypolyethylenepolypropyleneglycol mono (meth) acrylate, methoxypolyethylenepolybutyleneglycolmono (meth) acrylate, ethoxypolyethylenepolypropyleneglycolmono (meth) acrylate, ethoxypolyethylenepolybutyleneglycolmono (meth) acrylate, 1-propoxypolyethylenepolypropyleneglycolmono ( (Meth) acrylate, 1-propoxypolyethylene polybutylene glycol mono (meth) acrylate, 2-propoxypolyethylenepolypropylene glycol mono (meth) acrylate, 2-propoxypolyethylenepolybutylene glycol mono (meth) acrylate, 1-butoxypolyethylenepolypropylene glycol mono ( (Meth) acrylate, 1-butoxypoly Tylene polybutylene glycol mono (meth) acrylate, esterified product of (meth) allyl alcohol and (meth) acrylic acid with addition of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide, addition of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide Alkoxypolyalkylene glycol mono (meth) acrylates such as esterified products of alcohol and (meth) acrylic acid to which two or more alkylene oxides such as esterified products of crotyl alcohol and (meth) acrylic acid added are added Kind.

Examples of the monomer (b) that gives the structural unit (II) represented by the general formula (2) include acrylic acid, methacrylic acid, crotonic acid and their metal salts, ammonium salts, and amine salts. It is done. Particularly preferred are (meth) acrylic acid and salts thereof. The polycarboxylic acid copolymer (P-2) includes a monomer (for example, a monomer (c) described later) that provides the structural unit (III), and a monomer (for example, the structural unit (IV)). The monomer component containing a monomer (d)) described below as an essential component can be copolymerized and produced. Such a monomer component may further contain a monomer that gives the structural unit (V) (for example, a monomer (e) described later).

The ratio of each structural unit constituting the polycarboxylic acid copolymer (P-2) is, by mass ratio, structural unit (III) / structural unit (IV) / structural unit (V) = 1 to 99 /. It is preferable that it is 99-1 / 0-50. More preferably, the structural unit (III) / the structural unit (IV) / the structural unit (V) = 50 to 99/50 to 1/0 to 49, and more preferably the structural unit (III) / the structural unit (IV) / the structural unit. (V) = 60 to 95/40 to 5/0 to 30, most preferably the structural unit (III) / the structural unit (IV) / the structural unit (V) = 65 to 90/35 to 10/0 to 10. . However, the sum total of structural unit (III), structural unit (IV), and structural unit (V) is 100 mass%.

The polycarboxylic acid copolymer (P-2) is allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl. A monomer component containing an unsaturated alcohol such as -3-buten-2-ol and a monomer (for example, a monomer (d) described later) that gives the structural unit (IV) as an essential component is copolymerized. In addition, an average of 2 to 300 moles of alkylene oxide is added per mole of the unsaturated alcohol used for copolymerization, in other words, 1 mole of unsaturated alcohol constituent unit in the polymer, It can also be obtained by a method of reacting several 2-300 alkoxy polyalkylene glycols. In the general formula (3), the average addition mole number b of the oxyalkylene group is a number of 2 to 300, but a number of 5 to 300 is preferable. The number is more preferably 10 to 250, still more preferably 20 to 200, and particularly preferably 50 to 100. R ¹² is preferably a hydrogen atom, and the number of carbon atoms in the case of a hydrocarbon group is preferably 1 to 22. More preferably, it is 1-18, More preferably, it is 1-12, Especially preferably, it is 1-6, More preferably, it is 1-5, Most preferably, it is 1-3. Further, the number of carbon atoms of R ¹⁰ is 1 to 5, but 1 to 4 is preferable. More preferably, it is 1 to 3, and particularly preferably a structure of —CH ₂ —, — (CH ₂ ) ₂ —, or —C (CH ₃ ) ₂ —.

As the number of carbon atoms of the oxyalkylene group R ¹¹ O in the general formula (3), 2 to 18 is appropriate, but 2 to 8 is preferable. More preferably, it is 2-4. In addition, when it is one kind as the structural unit (III), it is preferable to have an oxyethylene group as an essential component in the oxyalkylene group in order to ensure a balance between hydrophilicity and hydrophobicity, more preferably 50 mol% or more. Particularly preferably, 60 mol% or more is an oxyethylene group. Examples of the monomer (d) that gives the structural unit (IV) represented by the general formula (4) include acrylic acid, methacrylic acid, crotonic acid and their metal salts, ammonium salts, amine salts and the like. Saturated monocarboxylic acid monomers; maleic acid, itaconic acid, citraconic acid, fumaric acid, or unsaturated dicarboxylic acid monomers such as metal salts, ammonium salts, and amine salts thereof. Furthermore, these anhydrides can also be used, for example, maleic anhydride, itaconic anhydride, citraconic anhydride and the like. In particular, it is preferable to use (meth) acrylic acid, maleic acid, maleic anhydride and salts thereof.

The monomer (e) that gives the structural unit (V) that can be used in the present invention is not particularly limited as long as it is a monomer copolymerizable with at least one of the other monomers. And the like. Half esters and diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid and alcohols having 1 to 30 carbon atoms; half of the unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms Amides and diamides: Half esters and diesters of alkyl (poly) alkylene glycols obtained by adding 1 to 500 moles of an alkylene oxide having 2 to 18 carbon atoms per mole of the alcohol or amine and the unsaturated dicarboxylic acids; Half esters and diesters of saturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or polyalkylene glycols having an average addition mole number of these glycols of 2 to 300.

Half amides of maleamic acid and glycols having 2 to 18 carbon atoms or polyalkylene glycols having an average addition mole number of these glycols of 2 to 300; triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) Acrylate, (poly) propylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate and other (poly) alkylene glycol di (meth) acrylates; hexanediol di (meth) acrylate, Multifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate and trimethylolpropane di (meth) acrylate; (poly) such as triethylene glycol dimaleate and polyethylene glycol dimaleate Ruki glycol dimaleate class.

Vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropyl sulfonate, 3- (meth) acryloxy-2 -Hydroxypropylsulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxybutylsulfonate, (meth) acrylamidomethylsulfonic acid, (meth) acrylamidoethylsulfonic acid, 2- Unsaturated sulfonic acids such as methylpropanesulfonic acid (meth) acrylamide and styrenesulfonic acid, and monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts (also referred to as organic ammonium salts); Acrylic acid, methacrylic acid, unsaturated monocarboxylic acids such as crotonic acid, and their metal salts, ammonium salts, amine salts.

1 to 30 carbon atoms and unsaturated monocarboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, glycidyl (meth) acrylate, methyl crotonate, ethyl crotonate, propyl crotonate Esters with alcohols; Amides of unsaturated monocarboxylic acids and amines having 1 to 30 carbon atoms such as methyl (meth) acrylamide; Vinyl aromas such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene Alkanediol mono (meth) acrylates such as 1,4-butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate; butadiene , Isoprene, 2-methyl-1,3 Dienes such as butadiene and 2-chloro-1,3-butadiene; unsaturated amides such as (meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide, and N, N-dimethyl (meth) acrylamide ; Unsaturated cyanides such as (meth) acrylonitrile and α-chloroacrylonitrile.

Unsaturated esters such as vinyl acetate and vinyl propionate; aminoethyl (meth) acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, (meth ) Unsaturated amines such as dibutylaminoethyl acrylate and vinyl pyridine; divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate; allyls such as (meth) allyl alcohol and glycidyl (meth) allyl ether ; Unsaturated amino compounds such as dimethylaminoethyl (meth) acrylate; methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono (meth) allyl ether, polyethyleneglycol Mono (meth) vinyl or allyl ethers such as allyl ether.

Polydimethylsiloxanepropylaminomaleamic acid, polydimethylsiloxaneaminopropylaminomaleamic acid, polydimethylsiloxane-bis- (propylaminomaleamic acid), polydimethylsiloxane-bis- (dipropylaminomaleamic acid), polydimethyl Siloxane- (1-propyl-3-acrylate), polydimethylsiloxane- (1-propyl-3-methacrylate), polydimethylsiloxane-bis- (1-propyl-3-acrylate), polydimethylsiloxane-bis- (1 Siloxane derivatives such as (propyl-3-methacrylate); unsaturated phosphate esters such as 2-acryloyloxyethyl phosphate and 2-methacryloyloxyethyl phosphate.

Polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine and malonic acid, succinic acid, fumaric acid, maleic acid, azelaic acid, sebacic acid Or a condensate of a dibasic acid such as an esterified product of these with an alcohol having 1 to 20 carbon atoms or an ester of a dibasic acid and an alcohol having 1 to 20 carbon atoms with (meth) acrylic acid or ( Alkylene oxide to a polyamide polyamine obtained by condensing an esterified product of (meth) acrylic acid with an alcohol having 1 to 20 carbon atoms, an unsaturated epoxy compound such as glycidyl (meth) acrylate and allyl glycidyl ether at a specific ratio. With a specific amount A compound obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to an active hydrogen of a polyalkyleneimine such as polyethyleneimine or polypropyleneimine and (meth) acrylic acid or (meth) acrylic acid and having 1 to 20 carbon atoms Cationic monomers having nitrogen atoms, such as esterified products with alcohols or condensed products with unsaturated epoxidized products such as glycidyl (meth) acrylate and allyl glycidyl ether.

The ultra-fine particle injection material composition of the present invention has the above-described structure, is excellent in dispersibility and dispersion retention, and has been impossible to inject due to the size of the particle size of conventional ultra-fine particle cement-based injection materials. The method for producing the ultra-fine particle injection material composition of the present invention can be easily injected into small particle gaps in the ground, rock cracks, and the like. Can be manufactured without the need for special equipment or a production line.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited only to these Examples.

The materials used are shown below.
<Materials used>
Ultra-fine particle cement: The ultra-fine particle cement was prepared by mixing and pulverizing the materials shown in Table 1 at a ratio shown in Table 2 and using a classifier to obtain a predetermined particle size.
The content (volume%) (particle amount) of particles of 1 to 5 μm described in Table 2 was measured after treatment for 3 minutes with an ultrasonic cleaner (output 40 W, frequency 40 kHz) using ethanol as a dispersion medium.
The content (volume%) (particle amount) of the above 1 to 5 μm particles represents the amount of particles in the range of 1 to 5 μm in particle size contained in the ultrafine particle cement, and is a laser diffraction particle size distribution measuring machine (Shimadzu Corporation). The amount of the powdery ultrafine particle cement was measured by SALD-2000J (refractive index: 1.70 ± 0.20i).

Dispersant: As the dispersant, the polycarboxylic acid dispersant and naphthalene sulfonic acid dispersant shown in Table 3 were used.
Dispersant c (also referred to as polycarboxylic acid copolymer (1) or copolymer (1)) and dispersant d (also referred to as polycarboxylic acid copolymer (2) or copolymer (2)). ) Was prepared by the following method, and the weight average molecular weight was measured. The measurement conditions are as follows.

(Weight average molecular weight measurement conditions)
Model: Waters LCM1, Detector: Waters 410 Differential refraction detector Analysis software: Waters Millenium Ver. 2.18, Eluent: 115.6 g of sodium acetate trihydrate is dissolved in a mixed solution of 10999 g of water and 6001 g of acetonitrile, and an eluent adjusted to pH 6 with 30% by mass sodium hydroxide is used. Eluent flow rate: 0.8 ml / min, column temperature 35 ° C., column: TSKgel Guard Column SWXL + G4000SWXL + G3000SWXL + G2000SWXL
Reference material: polyethylene glycol, weight average molecular weight (Mw) 272500, 219300, 85000, 46000, 24000, 12600, 4250, 7100, 1470

Production method of copolymer 1 (dispersant c) 99.8 g of water was charged into a glass reactor equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser, and the inside of the reaction vessel was stirred. The atmosphere was replaced with nitrogen and heated to 80 ° C. in a nitrogen atmosphere. When the internal temperature was stabilized at 80 ° C., 106.68 g of methoxypolyethylene glycol monomethacrylate (average number of added moles of ethylene oxide 25), 28.32 g of methacrylic acid, 33.75 g of water, and 1.46 g of 3-mercaptopropionic acid were mixed. The monomer aqueous solution 170.21 g was dropped into the reactor for 4 hours, and 30 g of an aqueous solution in which 1.62 g of ammonium persulfate was dissolved was dropped into the reactor in 5 hours. Thereafter, the temperature was continuously maintained at 80 ° C. for 1 hour to complete the polymerization reaction. After completion of the reaction, the mixture was neutralized with sodium hydroxide to obtain the polycarboxylic acid copolymer (1) of the present invention. The weight average molecular weight of the polycarboxylic acid copolymer (1) obtained in the present invention was 22,000.

Production method of copolymer 2 (dispersant d) Into a glass reactor equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser, 149.5 g of water was charged, and the inside of the reaction vessel was stirred. The atmosphere was replaced with nitrogen and heated to 80 ° C. in a nitrogen atmosphere. When the internal temperature was stabilized at 80 ° C., 47.41 g of methoxypolyethylene glycol monomethacrylate (average number of added moles of ethylene oxide 75), 12.58 g of methacrylic acid, 60.05 g of water, and 0.51 g of 3-mercaptopropionic acid were mixed. The monomer aqueous solution 120.51 g was added dropwise to the reactor for 4 hours and the aqueous solution 30 g of ammonium persulfate 0.69 g dissolved in 5 hours. Thereafter, the temperature was continuously maintained at 80 ° C. for 1 hour to complete the polymerization reaction. After completion of the reaction, the mixture was neutralized with sodium hydroxide to obtain the polycarboxylic acid copolymer (2) of the present invention. The weight average molecular weight of the polycarboxylic acid copolymer (2) obtained in the present invention was 30,500.

Examples, comparative examples and reference examples Examples and the like by the high-speed stirring process are shown below.
<Evaluation method>
Injection layer: The injection layer was filled with 534 g of glass beads (P-150, J-150 manufactured by Potters Barotini Co., Ltd., average particle size 90 μm) in an acrylic pipe of φ5.5 cm, and watertight so that the gap ratio was 40% by volume at a height of 15 cm. did. In addition, the minimum void | hole diameter by the calculated value at the time of the close packing of a glass bead layer is 14 micrometers, and the water permeability calculated | required from Hazen's approximate expression is 6.2 * 10 < ^-3 > cm / sec.

Slurry adjustment method: The slurry was adjusted by adding ultra-superfine cement to a solution obtained by adding a dispersant to water and stirring at a predetermined rotational speed for 3 minutes. It should be noted that the stirring is up to a peripheral speed of 628 m / min (stirring shaft rotation speed: 5000 rpm), a multipurpose digital stirrer (manufactured by Inoue Seieido Co., Ltd., stirring shaft maximum rotation speed: 5000 rpm, stirring blade diameter: 40 mm), A blender (manufactured by Oster Co., Ltd., stirring shaft maximum rotation speed 15700 rpm, stirring blade diameter 50 mm) was used.

Slurry injection: Slurry injection was carried out by natural infiltration by pouring 500 ml of slurry from the upper part of the injection layer.

Evaluation: The evaluation was performed based on the penetration length of the slurry and the time required for the slurry to pass through the injection layer. The results are shown in Table 4.

Example, examples and the like according to Comparative Examples and Reference Example 2-step hydrolysis stirring method are shown below.
<Evaluation method>
Slurry preparation method: The slurry is prepared by adding ultrafine cement to a solution obtained by adding a dispersant to water, and using a multipurpose digital stirrer (manufactured by Inoue Seieido Co., Ltd.) for initial stirring for 3 minutes at a peripheral speed of 75.4 m / min. After stirring at min (600 rpm), water was added so that the water / ultrafine particle cement mass ratio was 1000%, followed by stirring at a peripheral speed of 75.4 m / min (600 rpm). The injection layer and slurry injection and evaluation were performed in the same manner as in Example 1. The results are shown in Table 5.

In the above-described examples, ultra-fine particle cements 1, 2, and 5 to 8 are used as the ultra-fine particle cement, and the dispersants a, c, and d shown in Table 3 are used as the polycarboxylic acid-based dispersant. As long as it is a form formed by mixing a specific ultrafine particle cement in the invention and a polycarboxylic acid-based dispersant as essential components, the action mechanism for producing the effects of the present invention is the same. That is, the ultra-fine particle injection material composition has the essential features of the present invention in which at least the above-mentioned two components are essential. If these two components have similar chemical features, this example shows them. It will have an effect like this. Therefore, it can be said that the ultra-fine particle injection material composition constituted by the essential components in the present invention will surely exhibit the advantageous effects of the present invention. In the case where water is further contained, at least the advantageous effects of the present invention are sufficiently demonstrated by the above-described examples and comparative examples, and the technical significance of the present invention is supported.

Claims (5)

An ultra-fine particle injection material composition comprising an ultra-fine particle cement, a polycarboxylic acid dispersant and water as essential components,
The ultra-fine particle cement includes (a) 2 to 25% by mass of cement clinker having a content of 3CaO · Al ₂ O ₃ of 5% by mass or less, (b) 74 to 97% by mass of blast furnace slag, and (c) gypsum 1 Containing ~ 5% by weight,
The amount of particles having a particle size of 1 to 5 μm in the powder of the ultra-fine particle cement is 60 to 80% by volume,
The ultra fine particles injected material composition, hyper fine cement, a polycarboxylic acid dispersant and water as essential components, it der those obtained by stirring and mixing at a peripheral speed of 314m / min or more,
The polycarboxylic acid dispersant is represented by the following general formula (1):

(In the formula, R ¹ and R ² are the same or different and represent a hydrogen atom or a methyl group. R ³ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. The average addition mole number of an oxyalkylene group represents a number of 20 to 100. R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.) Unit (I) and the following general formula (2):

(In the formula, R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or a methyl group. M ¹ represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group). An ultra-fine particle injection material composition comprising a polycarboxylic acid copolymer (P-1) having a carboxylic acid structural unit (II) represented. A method for producing the ultrafine particle injection material composition according to claim 1,
The manufacturing method, possess hyper fine cement, a polycarboxylic acid dispersant and water as essential components, a high-speed stirring step of stirring and mixing at a peripheral speed of 314m / min or more,
The polycarboxylic acid dispersant is represented by the following general formula (1):

(In the formula, R ¹ and R ² are the same or different and represent a hydrogen atom or a methyl group. R ³ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. The average addition mole number of an oxyalkylene group represents a number of 20 to 100. R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.) Unit (I) and the following general formula (2):

(In the formula, R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or a methyl group. M ¹ represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group). A method for producing an ultrafine particle injection material composition comprising a polycarboxylic acid copolymer (P-1) having a carboxylic acid structural unit (II) represented . 3. The ultra-fine particle injection material composition according to claim 2 , wherein the production method comprises performing the high-speed stirring step after adding ultra-ultra fine particle cement to a solution obtained by adding a polycarboxylic acid-based dispersant to water. Manufacturing method. A method for producing an ultra-fine particle injection material composition obtained by mixing an ultra-fine particle cement, a polycarboxylic acid-based dispersant and water as essential components,
The ultra-fine particle cement includes (a) 2 to 25% by mass of cement clinker having a content of 3CaO · Al ₂ O ₃ of 5% by mass or less, (b) 74 to 97% by mass of blast furnace slag, and (c) gypsum 1 Containing ~ 5% by weight,
The amount of particles having a particle size of 1 to 5 μm in the powder of the ultra-fine particle cement is 60 to 80% by volume,
The production method includes an initial water stirring step in which ultra-fine particle cement, a polycarboxylic acid dispersant and water are mixed and stirred as essential components, and a second water stirring step in which water is further added and then stirred again after the step. And
The initial hydrolysis stirred water / hyper fine cement weight ratio in the process, Ri 40% to 60% der,
The polycarboxylic acid dispersant is represented by the following general formula (1):

(In the formula, R ¹ and R ² are the same or different and represent a hydrogen atom or a methyl group. R ³ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. The average addition mole number of an oxyalkylene group represents a number of 20 to 100. R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.) Unit (I) and the following general formula (2):

(In the formula, R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom or a methyl group. M ¹ represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group). A method for producing an ultrafine particle injection material composition comprising a polycarboxylic acid copolymer (P-1) having a carboxylic acid structural unit (II) represented . 5. The ultra-fine particle injection material according to claim 4 , wherein in the production method, after the ultra-fine particle cement is added to a solution obtained by adding a polycarboxylic acid-based dispersant to water, the initial water-hydration step is performed. A method for producing the composition.