JP4503403B2 - Rheology modifier - Google Patents

Description

  The present invention relates to a surfactant composition. In particular, it relates to a surfactant composition suitable as a rheology modifier for controlling slurry viscosity, and more specifically, contains powders used as civil engineering / building materials, secondary product materials, repair materials and the like. The present invention relates to a rheology modifier capable of imparting excellent properties such as viscosity to the water-powder slurry, and a surfactant composition capable of providing a slurry containing the modifier.

  In general, in order to control the rheological properties such as viscosity in a slurry of water and powder, the ratio of water and powder is adjusted, the dispersion state of particles is changed with a pH adjuster, or the water-absorbing polymer. Technology such as adding water to control the amount of surplus water has been used.

  In particular, the technology that adds water-soluble polymer compounds to the slurry system and uses the thickening action due to the entanglement of the polymer can be used for a wide range of applications, mainly in the civil engineering and construction fields, because it can provide a large thickening effect at low cost. It has become. For example, in Patent Document 1, cellulose derivatives such as methyl cellulose and hydroxyethyl cellulose, and in Patent Document 2, a water-soluble polymer compound such as poly (ethylene oxide) is used to increase the material separation resistance. Used for concrete and high fluidity concrete.

  However, in order to obtain an efficient thickening effect using a water-soluble polymer compound, it is necessary to use a compound having a molecular weight of a certain level or more, and the actually used compound has a molecular weight of several hundred thousand or more. Most are things. These water-soluble polymer compounds having a large molecular weight are added together with water and powder, and unless they are kneaded over time, it is difficult to develop sufficient viscosity, and a thickening effect cannot be obtained quickly. When used as, there is a problem that the viscosity of the aqueous solution is high and workability is lowered in terms of addition operation and the like.

  In addition, when water-soluble polymers are used in pastes, mortars, and concretes, there are many formulations with a small powder ratio (water powder ratio of 30% or more), and the viscosity with time increases as the water powder ratio increases. The stability of the material is reduced, and material separation such as breathing water is likely to occur.

  In the propulsion method, a drilling machine is attached to the tip of a propulsion pipe (reinforced concrete pipe, hard vinyl chloride pipe, steel pipe, cast iron pipe, etc.) manufactured at the factory, and the pipe is pressed into the ground with jacking propulsion, etc. It is a construction method for building a fence. The propulsion method is broadly divided into three methods: “blade edge propulsion method”, “sealed type propulsion method”, and “small-diameter pipe propulsion method”. In particular, there is a method called the mud pressure type propulsion method in the “sealed type propulsion method”, which mixes with the excavation sediment at the excavation head while injecting “drilling additive” that promotes plastic fluidization of the excavation sediment. Then, it is a construction method in which pressure is applied by the propulsion force of the main pushing jack, and the mud pressure is applied to the entire face to stabilize the face and to excavate while discharging with a screw conveyor. At this time, the “digging additive” promotes the ground with a large permeability coefficient of the excavated ground, a large amount of spring water, and a small amount of clay and silt in the ground (also referred to as fine particles, soil with a grain size of 0.075 mm or less). Is used when the soil cannot be drained smoothly due to the lack of fine particles even when the excavated soil and water are mixed, and the excavated soil with a large gap ratio and poor particle size balance is used as plastic fluidity. It has the role of remodeling it into an impermeable mud.

  Commonly known drilling additives include several types of clay with different particle sizes in water, water-soluble polymers as thickeners, and fibrous materials for water permeability control to impart material separation resistance and lubricity. Although it is composed of 5 to 10 kinds of materials and additives such as substances, lubricants, etc., the current state of technology is poor in water inseparability and viscoelasticity, and sufficient performance is not obtained. Furthermore, it is necessary to prepare from 5 to 10 or more kinds of materials, and the preparation of the additive becomes very complicated, and the quality control of the final additive becomes difficult in consideration of the fluctuation range of the performance of each material. Yes.

On the other hand, particularly with respect to a hydraulic composition, Patent Document 3 discloses a hydraulic composition that can increase the viscosity and fluidity of concrete and the like, and can provide properties excellent in aggregate, cement, and water material separation resistance. As additives for hydraulic use, there are described hydraulic composition additives formed by combining specific first and second compounds.
Japanese Patent Publication 5-39901 JP-A-11-189552 JP 2003-238222 A

  The additive of Patent Document 3 is said to be able to impart excellent separation resistance to the hydraulic composition that is a slurry. It has been found that there are cases where a sufficient reforming effect cannot be obtained.

  Then, this invention makes it a subject to provide the technique from which the outstanding rheology modification effect is acquired also with respect to the slurry containing clay.

The present invention relates to a cationic surfactant (hereinafter referred to as compound (A)) and one or more compounds selected from the group consisting of an anionic aromatic compound and bromide compound (hereinafter referred to as compound (B)). A surfactant composition containing a cationic polymer (C),
The combination of the compound (A) and the compound (B) is an aqueous solution S _A of the compound (A) (having a viscosity at 20 ° C. of 100 mPa · s or less) and an aqueous solution S _B of the compound (B) (viscosity at 20 ° C. Is a combination in which the viscosity at 20 ° C. of an aqueous solution mixed with a 50/50 weight ratio is at least twice as high as the viscosity of any aqueous solution (20 ° C.) before mixing. It relates to an activator composition.

  The present invention also includes a combination of a composition (A) containing the compound (A), a composition (B) containing the compound (B), and a composition (C) containing the cationic polymer (C). Or a composition (I) that contains any two of the compound (A), the compound (B), and the cationic polymer (C) and does not contain the remaining one, and the composition (I) The present invention relates to a kit for obtaining the surfactant composition of the present invention, comprising a combination with the composition (II) containing the remaining one that does not contain.

  The present invention also relates to a slurry containing the surfactant composition of the present invention, water, a filler other than hydraulic powder and / or clay, and clay.

  According to the present invention, a slurry rheology modifier containing the surfactant composition of the present invention (hereinafter sometimes referred to as the slurry rheology modifier of the present invention) can be provided. Moreover, according to this invention, the method of modifying the rheology of a slurry using the surfactant composition of the said invention can be provided.

  According to the present invention, a slurry rheology modifier capable of imparting excellent thickening property and proper material separation resistance to a slurry containing clay, such as a hydraulic composition, and obtaining an excellent rheology modification effect. A surfactant composition suitable for use in the present invention can be provided.

<Compound (A)>
Among the compounds (A), a quaternary salt type cationic surfactant is preferable as a compound selected from cationic surfactants, and the quaternary salt type cationic surfactant includes 10 to 26 in the structure. Those having at least one saturated or unsaturated linear or branched alkyl group containing one carbon atom are preferred. For example, alkyl (10 to 26 carbon atoms) trimethylammonium salt, alkyl (10 to 26 carbon atoms) pyridinium salt, alkyl (10 to 26 carbon atoms) imidazolinium salt, alkyl (10 to 26 carbon atoms) dimethylbenzylammonium salt Specific examples include hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium methosulfate, octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, tallow trimethylammonium chloride, tallow trimethylammonium bromide, hydrogen Tallow trimethylammonium chloride, hydrogenated tallow trimethylammonium bromide, hexadecylethyldi Examples include tillammonium chloride, octadecylethyldimethylammonium chloride, hexadecylpropyldimethylammonium chloride, hexadecylpyridinium chloride, 1,1-dimethyl-2-hexadecylimidazolinium chloride, hexadecyldimethylbenzylammonium chloride, and the like. Two or more kinds may be used in combination. Specifically, from the viewpoint of water solubility and thickening effect, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, hexadecylpyridinium chloride and the like are preferable. Further, from the viewpoint of thickening performance, two or more cationic surfactants having different alkyl chain lengths may be used in combination.

<Compound (B)>
Among the compounds (B), those selected from anionic aromatic compounds include carboxylic acids having an aromatic ring and salts thereof, phosphonic acids and salts thereof, sulfonic acids and salts thereof, specifically, salicylic acid, p-toluenesulfonic acid, sulfosalicylic acid, benzoic acid, m-sulfobenzoic acid, p-sulfobenzoic acid, 4-sulfophthalic acid, 5-sulfoisophthalic acid, p-phenolsulfonic acid, m-xylene-4-sulfonic acid, Cumene sulfonic acid, methyl salicylic acid, styrene sulfonic acid, chlorobenzoic acid, and the like. These may form a salt, and two or more of these may be used in combination. However, in the case of a polymer, the weight average molecular weight is preferably less than 500.

  Of the compounds (B), those selected from bromide compounds are preferably inorganic salts such as sodium bromide, potassium bromide, and hydrogen bromide.

<Cationic polymer (C)>
Examples of the cationic polymer (C) include a cationic polymer containing cationic nitrogen, a polymer having a quaternary salt structure in the molecule, and a cationic polymer in which the cationic nitrogen is quaternary nitrogen. .

  Examples of the cationic polymer (C) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, (meth) acrylamidoethyldimethylamine, (meth) acrylamidopropyldimethylamine, allylamine, allylmethylamine, allyldimethylamine. , Homopolymers such as diallylamine and diallylmethylamine, and copolymers obtained from these monomers and other monomers, both of which can be used as neutralized or non-neutralized types.

  In addition, as the cationic polymer (C), polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, and tripropylenetetramine, and alkylene oxides having 2 to 4 carbon atoms are added to the polyalkylenepolyamine. Any of neutralized type and non-neutralized type can be used.

  In addition, polyethyleneimine and a polymer obtained by adding a C2-C4 alkylene oxide to polyethyleneimine can be used as the cationic polymer (C).

  As the cationic polymer (C), those containing cationic nitrogen are preferable, and the cationic nitrogen of the cationic polymer further contains an alkyl group having 1 to 22 carbon atoms and an oxyalkylene group having 2 to 8 carbon atoms. A polyoxyalkylene group, a hydrogen atom and the following formula (1)

Wherein R _{1 to} R ₅ may be the same or different and each represents a hydrogen atom or an alkyl or alkenyl group having 1 to 22 carbon atoms, and Z is —O— or —NY—. (Y is a hydrogen atom or a C1-C10 alkyl group), and n is a number of 1-10. However, R ₁ and R ₃ may be incorporated into the polymer structure, in which case R ₁ and R ₃ are not present. A group to which a group selected from the above is bonded is preferable.

  Compounds derived from the group represented by the general formula (1) include methacryloyloxyethyltrimethylammonium salt, methacryloyloxyethyldimethylethylammonium salt, methacryloyloxypropyltrimethylammonium salt, methacryloyloxypropyldimethylethylammonium salt, methacrylamide Ethyltrimethylammonium salt, methacrylamideamidodimethylethylammonium salt, methacrylamideamidopropyltrimethylammonium salt, methacrylamidopropyldimethylethylammonium salt, acryloyloxyethyltrimethylammonium salt, acryloyloxyethyldimethylethylammonium salt, acryloyloxypropyltrimethylammonium salt, Acryloyloxypropyldimethyl Examples include tillammonium salt, acrylamidoethyltrimethylammonium salt, acrylamidoethyldimethylethylammonium salt, acrylamidopropyltrimethylammonium salt, acrylamidopropyldimethylethylammonium salt, and the like, and these are preferably alkyl sulfates, especially ethyl sulfate and methyl sulfate. .

  A polymer in which the cationic nitrogen of the cationic polymer (C) is derived from a diallyldialkylammonium salt, preferably a diallyldimethylammonium salt is also suitable. Specifically, a diallyldimethylammonium salt, an acrylic acid monomer, And the like.

  The cationic polymer (C) is a group consisting of a (meth) acrylic monomer having a cationic group, a styrene monomer having a cationic group, a vinylpyridine monomer, a vinylimidazoline monomer, and a diallyldialkylamine monomer. Those having a structure derived from a monomer selected from:

  Examples of the counter ion of the cationic polymer (C) include anionic ions such as halogen ions, sulfate ions, alkyl sulfate ions, phosphate ions, and organic acid ions.

Specific examples of the cationic polymer (C) include polyallyltrialkylammonium salts such as polyallyltrimethylammonium salt, poly (diallyldimethylammonium salt), polymethacryloyloxyethyldimethylethylammonium salt, and polymethacrylamidopropyltrimethylammonium salt. Cationized starch, cationized cellulose, cationized hydroxyethyl cellulose, etc., which may be obtained by polymerizing a monomer having a quaternary salt structure or obtained by quaternizing the corresponding polymer with a quaternizing agent. good. These may not be homopolymers, and may be a copolymer with a copolymerizable monomer as required. Specifically, diallyldimethylammonium salt-SO ₂ copolymer, diallyldimethylammonium salt-acrylamide copolymer, diallyldimethylammonium salt-acrylic acid-acrylamide copolymer, methacryloyloxyethyldimethylethylammonium salt-vinylpyrrolidone copolymer Examples thereof include a polymer and a methacrylamidopropyltrimethylammonium salt-vinylpyrrolidone copolymer. These may contain unreacted monomers, by-products, polymers of different cationization densities. These can be used in combination of two or more.

  Among the above, poly (diallyldimethylammonium salt), polymethacryloyloxyethyldimethylethylammonium salt, polymethacrylamidopropyltrimethylammonium salt, methacryloyloxyethyldimethylethylammonium salt-vinylpyrrolidone copolymer, and methacrylamidepropyltrimethylammonium salt -Cationic polymers selected from vinylpyrrolidone copolymers are preferred, and among these, from the viewpoint of the rheology modification effect, those in which the counter ion is an alkyl sulfate ion, among which ethyl sulfate and methyl sulfate are more preferred.

The molecular weight of the cationic polymer (C) is preferably 1000 or more, more preferably 1000 to 3 million, and is distinguished from the compound (A) in this respect. This molecular weight is a weight average molecular weight measured under the following conditions by gel permeation chromatography.
Column: α-M (manufactured by Tosoh Corp.) 2 linked Eluent: 0.15 mol / L Na sulfate 1% acetic acid aqueous solution Flow rate: 1.0 mL / min
Temperature: 40 ° C
Detector: RI
Pullulan is used as molecular weight standard

  The cationic polymer (C) has a cationization density of 0.5 to 10 meq / g, more preferably 1 to 9 meq / g, particularly 3 to 8 meq / g. To preferred. The cationization density can be measured by the method of Examples described later.

<Surfactant composition>
The compound (A) and compound (B) used in the surfactant composition of the present invention are an aqueous solution S _A having a viscosity of 100 mPa · s or less (20 ° C.) of the compound (A) and a viscosity of 100 mPa · s of the compound (B). When mixed with the aqueous solution S _B below (20 ° C.), it is necessary that the viscosity be at least twice as high as that of any aqueous solution before mixing (20 ° C.), preferably at least It can be 5 times higher, more preferably at least 10 times, even more preferably at least 100 times, particularly preferably at least 500 times higher.

  Here, the viscosity means that measured with a B-type viscometer (C rotor or No. 3 rotor, 1.5 rpm to 12 rpm) at 20 ° C. In this case, the viscosity behavior is 1.5 r. p. m. To 12r. p. m. It may be expressed at any of the number of rotations. Hereinafter, unless otherwise specified, the viscosity is measured under these conditions. Moreover, mixing mixes each aqueous solution by the weight ratio of 50/50. Furthermore, from the viewpoint of operability when adding the surfactant composition of the present invention to the slurry system, the viscosity at 20 ° C. of the aqueous solution of the compound (A) and the compound (B) before mixing is preferably 50 mPa · It is desirable to exhibit the same thickening effect when the two liquids are mixed at s or less, more preferably 10 mPa · s or less. In addition, the aqueous solution in which the compound (A) and the compound (B) are mixed is in a state in which a structure such as a single molecule, an aggregate, a micelle, or a liquid crystal is formed in water or a mixture thereof at room temperature. Is preferred.

  In the present invention, from the viewpoint that the compound (A) and the compound (B) easily form an aggregate, the compound (A) is selected from quaternary salt type cationic surfactants, and the compound (B ) Is particularly preferably a combination selected from anionic aromatic compounds. In this combination, each of the concentrated aqueous solutions has low viscosity, and when the slurry is a hydraulic composition, the effective component concentration of the compound (A) or the compound (B) in the hydraulic composition is 10% by weight. %, The viscosity is excellent even in a concentrated aqueous solution, which is preferable from the viewpoint of workability at the time of addition. In this combination, the material separation resistance of the hydraulic composition can be achieved with a low addition amount.

  Further, a combination in which the compound (A) is an alkyl (10 to 26 carbon atoms) trimethylammonium salt and the compound (B) is a sulfonate having an aromatic ring is particularly preferable when used as a slurry rheology modifier, When the slurry is a hydraulic composition, the effect is exhibited even when the effective component concentration in the aqueous phase of the hydraulic composition is 5% by weight or less. In particular, among these, from the viewpoint of not causing a curing delay, the compound (B) is preferably toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, styrenesulfonic acid or a salt thereof, particularly p-toluenesulfonic acid or a salt thereof. Salts are preferred.

  In the case where the surfactant composition of the present invention is used as a slurry rheology modifier, by using the compound (A), the compound (B) and the cationic polymer (C) in combination, the slurry containing clay is also used. It is considered that the excellent rheology modification effect is obtained for the following reason. That is, in the slurry in which clay is present, the compound (A) may be adsorbed on the clay to inhibit the formation of string micelles that play a role in rheology modification. However, when the cationic polymer (C) is present as in the present invention, the cationic polymer (C) is more easily adsorbed to the clay than the compound (A), so that the adsorption of the compound (A) to the clay is prevented. it can. Further, the adsorption of the cationic polymer (C) causes aggregation of clay particles, and the surface area of the clay is also reduced, so that the amount of the compound (A) adsorbed on the clay can be further reduced. As a result, string-like micelles (giant micelle aggregates) formed by the compound (A) and the compound (B) are sufficiently formed, and the original effects of the compound (A) and the compound (B) are maintained. It is done.

  In the present invention, when a sufficient rheology modification effect cannot be obtained by adsorption of the compound (A) to the clay, the cationic polymer (C) can prevent the adsorption of the compound (A) to the clay. In addition, it is considered that rheology modification is possible even when a substance having the ability to adsorb the compound (A) is present. As an index of the ability to adsorb the compound (A), it is preferable to apply to a substance having a chemical equivalent of 100 meg or more (0.1 meq / 100 g or more) with the compound (A), particularly 1 to 10 meq. The present invention is suitable for a substance of / 100 g because a predetermined rheology modification effect is hardly obtained even if the amount of compound (A) added is significantly increased. In addition, the chemical equivalent with this compound (A) can be measured by the method of the below-mentioned Example.

  In the surfactant composition of the present invention, for example, the compound (A), the compound (B) or the cationic polymer (C) is preferably 0.1 to 100% by weight, more preferably 1 to 100% by weight, Particularly preferably, preparations containing 5 to 100% by weight can be prepared and used by adding them to the slurry so that each compound has a ratio described later. Further, since the viscosity of the cationic polymer (C) does not increase even when mixed with the compound (A) or the compound (B), the cationic polymer (C) can be mixed with the compound (A) or the compound (B) in advance, and the charge of the same kind. It is preferable to mix with a compound (A) at the point which has.

  Since the compound (A) and the compound (B) are low in viscosity even in a concentrated aqueous solution of each compound alone, an aqueous solution is preferable. By making each effective concentration of the aqueous solution before addition to the slurry system preferably 10% by weight or more, more preferably 20% by weight or more, further preferably 30% by weight or more, and most preferably 40% by weight or more, Productivity can be improved, such as the size of the storage tank being reduced.

  Other surfactants can be used in combination with the surfactant composition of the present invention. Other surfactants are preferably amphoteric surfactants and nonionic surfactants. In particular, betaine compounds and compounds obtained by adding alkylene oxide to alcohol are preferred.

  The surfactant composition of the present invention can be used in combination with a solvent for viscosity adjustment and the like. As the solvent, alcohol or cellosolve type solvent is preferable, and propylene glycol is preferable from the viewpoint of rheology modification effect and flash point.

  The surfactant composition of the present invention may contain other components such as a dispersant, an AE agent, a retarder, an early strengthening agent, an accelerator, a foaming agent, a foaming agent, an antifoaming agent, a rust inhibitor, depending on the application. Coloring agents, antifungal agents, crack reducing agents, swelling agents, dyes, pigments, scale inhibitors, slime treatment agents, preservatives, emulsifiers and the like may be contained. The slurry rheology modifier containing the surfactant composition of the present invention may also contain these components.

  Since a slurry having a modified rheology can be obtained by adding the compound (A), the compound (B) and the cationic polymer (C) to the slurry, the surfactant composition of the present invention is used for the rheology modification of the slurry. Therefore, the form of addition of each component when used for the purpose is not particularly limited.

  In the surfactant composition according to the present invention, even when the compounds (A) and (B) are in the state of an extremely low viscosity aqueous solution, a large viscosity is exhibited when mixed. Therefore, for the rheology modification of the slurry, it is preferable to use the compound (A) and the compound (B) in an aqueous solution and add the cationic polymer (C) at an appropriate location. At this time, from the viewpoint of operability, when added to the slurry system, each of the aqueous solution of the compound (A) and the aqueous solution of the compound (B) is 100 mPa · s or less, preferably 50 mPa · s or less, at the temperature used. It is preferably used in the state of an aqueous solution having a viscosity of 10 mPa · s or less.

  When the surfactant composition of the present invention is used to modify the rheology of the slurry, the molar ratio (effective molar ratio) of the compound (A) to the compound (B) depends on the intended degree of thickening. However, from the viewpoint of the viscosity obtained and the shape of the aggregate, compound (A) / compound (B) = 1/20 to 4/1, preferably 1/3 to 2/1, particularly preferably 1/1 to 2/3 is suitable. The molar ratio here is calculated as [total number of moles of all compounds belonging to compound (A)] / [total number of moles of all compounds belonging to compound (B)].

  Moreover, it is preferable that a cationic polymer (C) is used in the ratio of 1-500 weight part with respect to 100 weight part of compounds (A), Furthermore, 5-400 weight part, Especially 8-300 weight part.

  The compound (A), the compound (B) and the cationic polymer (C) in the present invention may be used either in an aqueous solution or in a powder state, and particularly in any form in the surfactant composition of the present invention. Good slurry rheological properties can be imparted. When the compound (A), the compound (B) and the cationic polymer (C) are used in the form of powder in advance, workability in premix applications and the like is improved. However, considering that the slurry can be adjusted to a desired viscosity, the compound (A), the compound (B) and the cationic polymer (C) are not subjected to surface treatment in advance on the filler which is a constituent powder of the slurry. The method is preferred.

  According to the present invention, there is provided a slurry containing the surfactant composition of the present invention, water, a filler other than hydraulic powder and / or clay, and clay. The slurry can also contain a slurry rheology modifier containing the surfactant composition of the present invention.

  The hydraulic powder is a powder having physical properties that hardens by a hydration reaction, and examples thereof include cement and gypsum. Examples thereof include hydraulic powder cement and gypsum such as ordinary Portland cement, moderately hot cement, early strong cement, very early strong cement, high belite-containing cement, blast furnace cement, fly ash cement, alumina cement, and silica fume cement.

  Examples of the filler include calcium carbonate, fly ash, blast furnace slag, and silica fume. These powders may be used alone or in combination. Furthermore, sand, gravel, and a mixture thereof may be added to these powders as aggregates as necessary. Moreover, it can also apply to inorganic oxide type powders other than the above, such as titanium oxide, and soil.

  The clay is mainly composed of a hydrous silicate mineral with a layered structure (hereinafter referred to as clay mineral). The clay mineral contained as a fine mineral in this clay is kaolin mineral (kaori mineral). Knight, dickite and nacrite), serpentine (lizardite, antigolite, chrysotile), mica clay minerals (illite, sericite, sea chlorite, celadonite), chlorite, vermiculite, smectite (montmorillonite, beidellite, nontronite), Saponite, hectorite). Examples of clays composed of these clay minerals include fuller's earth, ball clay, refractory clay, ceramic stone, talc, and pyrophyllite. Moreover, chemical treatment, for example, acid clay treated with heat treatment and alkali treatment, Na bentonite, Ca bentonite, and the like are also included. In production areas, purified bentonite used in cosmetics and artificially made clay include synthetic mica, synthetic kaolinite, and synthetic smectite. In addition, Kasaoka clay (trade name: manufactured by Kanesan Kogyo Co., Ltd.) used in civil engineering materials can be mentioned. These clays may be used alone or in combination with various clays. In addition to the above-mentioned clay mineral as a main component, the clay referred to in the present invention includes those coexisting with fillers other than clay and those present in aggregates such as sand.

  The soil is roughly classified into sandy soil having a small amount of clay and viscous soil having a large amount of clay. The soil is a mixture of inorganic materials such as clay and organic materials such as humus and organisms. There are many different types of soil, and their definitions differ depending on the target academic field. However, the soil used in this application is geologically residual soil and transported soil. Non-synthetic soil, interstitial soil. As familiar examples, “Fujisuna”, “Kanuma-do”, “Akatama” for gardening, and the like can be cited as soil.

  The slurry of the present invention can contain a water reducing agent, and in addition to a general water reducing agent, a high performance water reducing agent and a high performance AE water reducing agent are preferable. As a high-performance water-reducing agent and a high-performance AE water-reducing agent (hereinafter referred to as a high-performance water-reducing agent, etc.), naphthalene-based (manufactured by Kao Corporation: Mighty 150), melamine-based (manufactured by Kao Corporation: Mighty 150V-2), Examples thereof include polycarboxylic acid-based products (manufactured by Kao Corporation: Mighty 3000, manufactured by NMB: Leo Build SP, manufactured by Nippon Shokubai Co., Ltd .: Aqualock FC600, Aqualock FC900). As these high-performance water reducing agents, polycarboxylic acids are desirable from the viewpoint that when they coexist with the compound (A) and the compound (B), the influence on the viscosity and dispersibility of the concrete is small. The amount of the high-performance water reducing agent used is preferably 0.1 to 5% by weight, more preferably 1 to 3% by weight, based on the hydraulic powder.

  Moreover, the slurry of this invention can contain an aggregate. Aggregates include coarse aggregates and fine aggregates, and any of those generally used in the field of hydraulic compositions can be used. The amount of aggregate is not particularly limited, but coarse aggregate 250-400L and fine aggregate 250-400L are suitable in 1000L of slurry. In addition to fine aggregates usually used in the field of hydraulic compositions, earth, sand, gravel, and gravel that contain the above-mentioned clay capable of adsorbing the compound (A) used in the civil engineering field. Even when sand, silt or the like is used as an aggregate, the surfactant composition of the present invention can be used without impairing the viscoelasticity of the aggregate.

  The slurry preferably has a water powder ratio [weight percentage of water and powder in the slurry (% by weight)] of 30 to 300%. In particular, in the case of a hydraulic composition, it is preferably 35 to 250%, more preferably 40 to 200% by weight. Moreover, the powder used for a slurry may be individual or mixed.

  Also, the surfactant composition of the present invention or the present invention is prepared by premixing one or more compounds selected from the compound (A), the compound (B) and the cationic polymer (C) in the present invention with a hydraulic powder. It is also possible to prepare a hydraulic powder composition containing the slurry rheology modifier.

  When the surfactant composition of the present invention is added to the slurry, the compound (A), the compound (B) and the cationic polymer (C) can be added to the slurry in any order, but the compound (A) and the compound (B ) Is added to the slurry, the other compound is added to the slurry, and the cationic polymer (C) can be added at an arbitrary location. For example, one of the compound (A) and the compound (B) is added to the slurry at an appropriate stage, and the other is added to the slurry at a stage where viscosity is required. The addition with A) or compound (B) is preferable from the viewpoint of workability. Further, the cationic polymer (C) may be used by mixing in advance with one or both of the compound (A) and the compound (B). The state of the compound (A), the compound (B), and the cationic polymer (C) when added to the slurry may be liquid or powder. A kit comprising a combination of a composition (A) containing compound (A), a composition (B) containing compound (B), and a composition (C) containing cationic polymer (C), or Of the compound (A), the compound (B), and the cationic polymer (C), the composition (I) that includes any two and does not include the remaining one, and the remaining one that does not include the composition (I) The kit comprising the combination with the composition (II) containing one can be suitably used for a method for modifying the rheology of the slurry. These kits can contain a composition other than these compositions as required.

  In addition, the surfactant composition of the present invention can be added during slurry production. For example, first, a slurry containing one compound (A) or (B), a cationic polymer (C), a powder, for example, a hydraulic powder such as cement, and water, is prepared, The method of adding the other compound of the said compound (A) or (B) to a slurry is mentioned.

  In particular, when the surfactant composition of the present invention is used in a slurry system using hydraulic powder such as cement, the hydration reaction of cement particles can be controlled, and entrained bubbles during slurry stirring are suppressed. From the viewpoint, it is preferable that the compound (A) or the compound (B) and the cationic polymer (C) are added to the slurry first, and the remaining compound (B) or the compound (A) is added later. .

  In any case, the total effective amount of the compound (A) and the compound (B) is 0.01 to 20% by weight, more preferably 0.1 to 15% by weight, particularly 0.1% in terms of the effective concentration in the aqueous phase of the slurry. It is preferable to use it so that it may become 10 to 10 weight%. The cationic polymer (C) is used so that it is 1 to 500 parts by weight, more preferably 5 to 400 parts by weight, and particularly 8 to 300 parts by weight with respect to 100 parts by weight of the compound (A) in the aqueous phase of the slurry. It is preferable.

The slurry of the present invention can be used for various applications depending on the powder, but is preferably used as a drilling additive for the propulsion excavation method, and the composition of the additive (slurry) is a filler other than clay, In particular, fly ash is preferable, and the additive (slurry) density is 1.055 to 1.385 g / cm ³ (water powder ratio 970 to 100), and 1.161 to 1.318 g / cm ³ (water powder). Body ratio 300-130) is preferred (e.g., calculated as a fly ash density of 2.25 g / cm < ³ >).

  The slurry of the present invention can be applied as an additive as described above. In particular, the excavation ground can be prevented from collapsing due to the excellent viscoelasticity according to the present invention, water loss can be prevented, water can not be separated, and gravel can be prevented from clogging. The slurry of the present invention maintains its effect during construction by the effect of the cationic polymer (C) even when a large amount of clay to which the compound (A) is adsorbed is contained. In addition, when the slurry of the present invention is used as an additive, the additive alone has high material separation resistance, viscosity increase, lubricity, and water permeation suppressing effect, so that the number of materials can be reduced. As a blending example, water and a filler other than clay, for example, one kind of powder selected from fly ash, calcium carbonate, blast furnace slag, and silica fume, and the surfactant composition of the present invention are sufficient as a drilling additive. Performance.

<Example 1>
(1) Slurry raw material The following were used as slurry raw materials.
・ Hydraulic powder: Ordinary Portland cement, density 3.16 g / cm ³ , Taiheiyo Cement Co., Ltd.Compound (A): Hexadecyltrimethylammonium chloride / octadecyltrimethylammonium chloride = 50/50 (weight ratio) mixture [29 wt. % Aqueous solution (used as a viscosity of 18 mPa · s at 20 ° C.)]
Compound (B): sodium p-toluenesulfonate [used as a 20% by weight aqueous solution (viscosity at 20 ° C., 2.5 mPa · s)]
・ Clay: Kasaoka Clay (Kanesan Industry Co., Ltd.)
Additive: Table 1 In addition, the viscosity at 20 ° C. of an aqueous solution in which a 29 wt% aqueous solution of compound (A) and a 20 wt% aqueous solution of compound (B) are mixed at a weight ratio of 50/50 is 200,000. mPa · s.

(2) Preparation of slurry 400 g of cement, 20 g of clay, 400 g of water containing compound (B) and the additives shown in Table 1 [8 g of aqueous solution of compound (B) (2% by weight based on the total weight of water) 1) is added for 30 seconds with a hand mixer, and then 8 g of the aqueous solution of the compound (A) (total weight of 2% by weight of the water) is mixed with this, and then for 60 seconds with a hand mixer. Mixed.

(3) Evaluation The viscosity of the obtained slurry was measured immediately after preparation (after 0 minutes), after 60 minutes, and after 120 minutes. The viscosity was measured at 20 ° C. using a Viscotester manufactured by Rion (using a No. 1 rotor). The results are shown in Table 1. As shown in Table 1, Comparative Product 1 has a large decrease in slurry viscosity over time, and Comparative Products 2 to 6 result in separation of the slurry. On the other hand, none of the products of the present invention has a stable slurry viscosity with time and does not cause separation. Here, the separation of the slurry means that a part of the water in the slurry separates from the powder and aggregate and floats on the upper layer of the slurry.

(Note) The weight% of the additive in the table is the weight% of the effective part of the additive with respect to the effective part of the compound (A). Each polymer is as follows.
Cationic polymer (1): poly (diallyldimethylammonium chloride), manufactured by Aldrich, low molecular weight product (weight average molecular weight 5000-20000 (labeled)), cationization density 6.13 meq / g (40% by weight as aqueous solution) Using)
Cationic polymer (2): poly (diallyldimethylammonium chloride), manufactured by Aldrich, weight average molecular weight 100,000 to 200,000 (labeled), cationization density 6.19 meq / g (used as 20 wt% aqueous solution)
Cationic polymer (3): poly (diallyldimethylammonium chloride), manufactured by Aldrich, weight average molecular weight 400,000 to 500,000 (labeled), cationization density 6.15 meq / g (used as 20% by weight aqueous solution)
Cationic polymer (4): polymethacryloyloxyethyldimethylethylammonium ethyl sulfate, weight average molecular weight 120,000, cationization density 3.63 meq / g (used as 36.5 wt% aqueous solution)
Cationic polymer (5): diallyldimethylammonium chloride-SO ₂ copolymer, weight average molecular weight 4000, trade name PAS-A-5 (Nittobo Co., Ltd.), cationization density 4.33 meq / g
Cationic polymer (6): trade name Aclac 41 (Mitsui Cytec Co., Ltd.), weight average molecular weight 40,000, cationization density 7.10 meq / g (used as 50 wt% aqueous solution)
Cationic polymer (7): trade name Acurac 35 (Mitsui Cytec Co., Ltd.), weight average molecular weight 70,000, cationization density 7.11 meq / g (used as 50 wt% aqueous solution)
Cationic polymer (8): trade name Acurac 57 (Mitsui Cytec Co., Ltd.), weight average molecular weight 250,000, cationization density 7.27 meq / g (used as 50 wt% aqueous solution)
Cationic compound: tetramethylammonium chloride (reagent), molecular weight 109.6, cationization density 9.12 meq / g (effective content 100%)
-Polymer (1): Carboxymethylcellulose, trade name CMC1190 (Daicel Chemical Industries, Ltd.)
-Polymer (2): Polyvinylpyrrolidone, trade name K-60 (ISP TECHNOLOGIES INC.)

The cationization density measurement (colloidal titration) of the cationic polymer was performed as follows.
First, a cationic polymer (form may be pure or solution) is dissolved in water adjusted to pH 3.0 with phosphoric acid. Toluidine blue indicator was added and titrated with 1 / 400N polyvinyl potassium sulfate solution. The cationization density was determined by the following calculation formula.
Cationization density (meq / g) = 1/400 × f × (mL) / 1000 × 1000 × 1 / [(g) × (%) / 100]
f: Factor of 1 / 400N polyvinyl potassium sulfate solution
(mL): dripping amount of polyvinyl potassium sulfate solution
(g): Sample amount
(%): Sample concentration

<Example 2>
Using the compound (A), compound (B), and additives used in Example 1, a slurry suitable as a drilling additive for the propulsion method was prepared. That is, fly ash [commercial product (manufactured by Kansai Electric Power Co., Inc.), density 2.25 g / cm ³ ] 100 g and water (155 g) containing compound (B) and additives shown in Table 2 [compound (B) aqueous solution 2.33 g ( And 1.5% by weight based on the total weight of water) and an additive in the amount shown in Table 2). 1.5% by weight with respect to the total weight of water) and mixed for 60 seconds with a hand mixer to obtain a slurry. The slurry had a water powder ratio of 150% and a density of 1.286 g / cm ³ .

A model soil (bulk density: 1.087 g / cm ³ ) was prepared assuming sandy soil in which Kasaoka clay and mountain sand from Kimitsu, Chiba Prefecture were mixed at a weight ratio of 1: 3. The obtained slurry and model soil were mixed so that the weight ratio of slurry / model soil was 1.0 or 2.0, and stirred with a hand mixer for 60 seconds. Immediately after preparation of the mixture (after 0 minutes), 60 minutes later, the viscosity at 20 ° C. was measured with a B-type viscometer (rotation speed: 6 rpm). The results are shown in Table 2. As shown in Table 2, in the slurry / model soil mixed system of Comparative products 2-1, 2-2, the viscosity does not increase with time, whereas in the product of the present invention, the viscosity is remarkably increased with time. It is increasing.

<Example 3>
(1) Concrete mix

Cement (C): Ordinary Portland cement (commercial product, density 3.16 g / cm ³ )
Stone powder: Calcium carbonate powder (Shimizu Kogyo, density 2.72 g / cm ³ )
Sand 1: Crushed sand from Hyogo Prefecture (density 2.57g / cm ³ )
Sand 2: Sea sand from Saga (density 2.57 g / cm ³ )
High-performance water reducing agent: Polycarboxylic acid-based high-performance water reducing agent “Mighty 3000” [manufactured by Kao Corporation]

(2) Preparation of mortar The compound used in Example 1 was charged with cement (C) and fine aggregate (S) using a mortar mixer under the blending conditions shown in Table 3, and kneaded for 10 seconds. (B), kneading water (W) containing the high performance water reducing agent and the additive used in Example 1 was added and stirred for 30 seconds, and then the compound (A) used in Example 1 was added and kneaded for 90 seconds. did. Immediately after preparation of the obtained mortar (after 0 minutes), fluidity and viscosity were measured after 20, 40 and 60 minutes. The fluidity was measured by measuring the diameter of a mortar that had been stuffed into a mortar cone and pulled up vertically. The viscosity was measured at 20 ° C. using a Rion viscotester (using No. 1 rotor). The compound (A) and the compound (B) were 4.0% by weight with respect to the total weight of the kneaded water, and the amounts of the additives were as shown in Table 4. The sand 1 and sand 2 used in this example are fine aggregates containing a large amount of fine particles such as clay, and have the ability to adsorb the compound (A) [hereinafter referred to as compound (A) adsorbing ability]. Were 1.3 meq / 100 g and 1.2 meq / 100 g, respectively. Here, the compound (A) adsorption capacity was determined as follows.

As the compound (A), a 29% by weight aqueous solution of a mixture of hexadecyltrimethylammonium chloride and octadecyltrimethylammonium chloride (weight ratio 50:50, molecular weight 330.71) was used. This compound (A) aqueous solution 8.2g was diluted with water, adjusted to 200mL, put into an 800mL glass bottle with a lid (made by Hoshi Glass Co., Ltd.) together with 400g of the test substance (sand), and shaken by hand for 10 seconds. . Thereafter, the mixture was allowed to stand for 50 seconds, and the supernatant was collected. The residual concentration of compound (A) in the supernatant was determined by a calibration curve method using a TOC (total organic carbon analyzer). From the residual concentration α (mg / L), the compound (A) adsorptive capacity was determined from the following calculation formula.
Compound (A) adsorption capacity [meq / 100g] = [(8.2 × 0.29 × 1000) −α × 0.2] ÷ 400 ÷ 330.71 × 100

  In Comparative Products 3-1, 3-2, material separation was observed after 20 minutes. On the other hand, the products 3-1 to 3-3 of the present invention are useful as a drilling additive for a propulsion method, for example, because material separation with time does not occur and fluidity and viscosity change little with time.

Claims (6)

One or more compounds selected from the group consisting of a cationic surfactant (excluding the cationic polymer (C)) (hereinafter referred to as compound (A)), an anionic aromatic compound and a bromide compound (hereinafter referred to as compound) (B)) and a clay containing a cationic polymer (C) containing cationic nitrogen, having a weight average molecular weight of 1000 or more and a cationization density of 0.5 to 10 meq / g. An applied rheology modifier,
The combination of the compound (A) and the compound (B) is an aqueous solution S _A of the compound (A) (having a viscosity at 20 ° C. of 100 mPa · s or less) and an aqueous solution S _B of the compound (B) (viscosity at 20 ° C. Is a combination in which the viscosity at 20 ° C. of an aqueous solution mixed with a 50/50 weight ratio is at least twice higher than the viscosity of any aqueous solution (20 ° C.) before mixing,
The cationic nitrogen of the cationic polymer (C), a polyoxyalkylene group comprising an alkyl group having 1 to 22 carbon atoms, an oxyalkylene group having 2 to 8 carbon atoms, a hydrogen atom, and the following formula (1)

Wherein R _{1 to} R ₅ may be the same or different and each represents a hydrogen atom or an alkyl or alkenyl group having 1 to 22 carbon atoms, and Z is —O— or —NY—. (Y is a hydrogen atom or a C1-C10 alkyl group), and n is a number of 1-10. However, R ₁ and R ₃ may be incorporated into the polymer structure, in which case R ₁ and R ₃ are not present. And a group selected from
The cationic polymer (C) is selected from the group consisting of a (meth) acrylic acid monomer having a cationic group, a styrene monomer having a cationic group, a vinylpyridine monomer, a vinylimidazoline monomer, and a diallyldialkylamine monomer. Having a structure derived from the monomer
Rheology modifier.   The rheology modifier according to claim 1, wherein the cationic nitrogen of the cationic polymer (C) is quaternary nitrogen.   The rheology modifier according to claim 1 or 2, wherein the cationic nitrogen of the cationic polymer (C) is derived from a diallyldimethylammonium salt. A combination of the composition (A) containing the compound (A), the composition (B) containing the compound (B) and the composition (C) containing the cationic polymer (C), or Of the compound (A), the compound (B), and the cationic polymer (C), the composition (I) that includes any two and does not include the remaining one, and the remaining one that does not include the composition (I) The kit for obtaining the rheology modifier in any one of Claims 1-3 which comprises the combination with the composition (II) containing two. The slurry containing the rheology modifier in any one of Claims 1-3 , water, fillers other than hydraulic powder and / or clay, and clay. The slurry according to claim 5, which is used as a drilling additive for a propulsion method.