JP2003313536A - Slurry rheology modifier - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a slurry rheology modifier capable of imparting excellent rheological properties, e.g. viscosity, material segregation resistance to slurry. <P>SOLUTION: The slurry rheology modifier comprises (A) a 1st water-soluble low-molecular compound and (B) a 2nd water-soluble low-molecular compound, wherein the viscosity at 20°C of an aqueous solution prepared by equally mixing the aqueous solution of the compound A and that of the compound B together is at least twice higher than that of each of the aqueous solutions. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rheology modifier for controlling slurry viscosity, and more specifically, it contains powders used as civil engineering / building materials, secondary product materials and repair materials. To water-powder slurry,
The present invention relates to a rheology modifier capable of giving properties excellent in viscosity and material separation resistance, and a method for producing a slurry by adding the modifier.

[0002]

2. Description of the Related Art Generally, in order to control rheological properties such as viscosity in a slurry composed of water and powder, the ratio of water to powder is adjusted, the dispersion state of particles is changed by a pH adjuster, etc. Alternatively, techniques such as adding a water-absorbing polymer to control the amount of surplus water have been used.

In particular, the technique of adding a water-soluble polymer compound to a slurry system and utilizing the thickening effect by the entanglement of polymers can obtain a large thickening effect at a low cost, so that it is widely used mainly in the fields of civil engineering and construction. Has been put to practical use. For example, cellulose derivatives such as methyl cellulose and hydroxyethyl cellulose [Japanese Patent Publication No. 5-39901] and poly (ethylene oxide) [JP-A-11-189452].
No.] is used in pastes, mortars, underwater concretes, and high-fluidity concretes in order to increase the resistance to separation of materials.

However, in order to obtain an effective thickening effect by using a water-soluble polymer compound, it is necessary to design a molecular weight above a certain level, and the actually used compound has a molecular weight of several hundred thousand. Most of the above. These water-soluble polymer compounds having a large molecular weight are difficult to develop sufficient viscosity unless they are added together with water and powder and kneaded for a long time, and there is a problem in the case of rapidly obtaining an effect.
Further, if it is used as an aqueous solution in advance, the viscosity of the aqueous solution increases, which causes problems in addition operation and workability, which is not realistic. Further, when a water-soluble polymer compound is used for the hydraulic powder, there is a problem that curing delay occurs. Further, since these water-soluble polymers are polymerized by covalent bonds, there is a problem that the bonds are deteriorated by repeated shearing force in an aqueous solution system and eventually cut. Especially in a slurry containing powder, a strong shearing force is exerted on the water-soluble polymer due to the strong friction caused by the powder during stirring and pressure feeding, so that the molecular weight is more likely to decrease due to deterioration than the aqueous system. There is also a problem that the performance cannot be exhibited.

Generally, when a water-soluble polymer is used in pastes, mortars and concrete, the proportion of the powder is small (water powder ratio is 30% or more), and the proportion of the water powder is large. The stability of viscosity over time decreases,
Breathing water comes out and material separation occurs.

Further, when it is desired to make an aqueous slurry system coexist with the aqueous phase, the conventional technique elutes the slurry system into the aqueous phase,
In some cases, the initial slurry composition could not be maintained. In the field of construction and civil engineering, for example, in so-called underwater concrete intended for pouring in lakes or the sea, sufficient isolation resistance in water cannot be obtained by simply adding a water-soluble polymer compound. Alkali metal sulfate is used in combination as in JP-A 3-38224. However, the alkali metal salt causes a decrease in the compressive strength of the concrete and a marked decrease in the fluidity depending on the amount added, making it difficult to produce concrete of stable quality and high resistance to separation in water. Furthermore, cement powder, which is most often used in the field of civil engineering and construction, becomes strongly alkaline with pH of 11 or more when it comes into contact with water, and at the same time, even if it is a W / C = 100% slurry, it has a strong ionic conductivity of 10 mS / cm or more. Since it becomes an electrolyte slurry, the dispersion of the slurry in water has a great influence on the natural environment, which has been a factor causing water pollution. Also, in the case of the grout method of injecting cement paste (so-called cement milk) with a high water powder ratio into the ground for soil improvement, when groundwater springs out, the composition of cement milk becomes unstable and As mentioned above, there is a problem of load on the natural environment such as underground and surrounding rivers. Further, when a copolymer is used as the polymer compound, there is a problem that the dispersed state of the slurry is easily affected.

As a technique of using a surfactant to improve fluidity, there is a thickener combination for building materials disclosed in JP-A-7-166150. This is a combination system of a nonionic cellulose ether, which is a polymer compound, and the viscosity itself can be increased, but the resistance to separation of breathing water or water has not been improved.

In addition, when a slurry or concrete to which a water-soluble polymer is added and which has high resistance to material separation is pumped, the viscosity of the water-soluble polymer prevents the pump from being pumped, or a predetermined pressure is fed. In some cases, the speed could not be obtained.

On the other hand, a study on the viscosity of a simple aqueous solution system has been reported [Surface Vol.29, No. 5 (1991) p. 61].
It describes the viscosity behavior of string micelles of a system in which sodium salicylate (or salicylic acid) is added to an aqueous cetyltrimethylammonium bromide solution.

[0010]

According to the present invention, even when prepared in advance as an aqueous solution, the viscosity of the aqueous solution is low and there is no problem in workability, and a sufficient viscosity can be obtained by kneading in a short time when producing a slurry. Furthermore, the material separation resistance is stable,
A slurry rheology modifier for obtaining a slurry that has stable properties and composition even when the water-powder ratio is high or when it comes into contact with the aqueous phase, and that does not delay the setting of the hydraulic powder and has excellent cured physical properties. The challenge is to provide.

[0011]

Means for Solving the Problems The present inventors have solved the above problems by using a slurry rheology modifier containing two kinds of different water-soluble low molecular weight compounds satisfying specific properties. I found it.

The first aspect of the present invention is to provide a first water-soluble low molecular compound [hereinafter referred to as compound (A)] and a second water-soluble low molecular compound different from compound (A) [hereinafter referred to as compound (A)]. (B)], which is an aqueous solution S _A of the compound (A) (having a viscosity of 100 mPa · s or less at 20 ° C.) and an aqueous solution S _B of the compound (B). 20 of an aqueous solution in which the viscosity at 20 ° C. is 100 mPa · s or less) is mixed at a weight ratio of 50/50.
It relates to a slurry rheology modifier whose viscosity at 0 C can be at least 2 times higher than the viscosity of any aqueous solution before mixing.

Here, the water-soluble low-molecular weight compound is phase-separated from water in a state where a single molecule or a structure such as an associate, a micelle, a liquid crystal is formed in water or a mixture thereof at room temperature. It is a compound that does not occur. A phase is a region having a macroscopic size and in which statistical physical quantities such as temperature and pressure are clearly defined (Colloidal Chemistry, Volume 1, First Edition, 8
9-90, issued October 12, 1995, Tokyo Kagaku Dojin).

Further, the aqueous solution of the compound (A) and the aqueous solution of the compound (B) are those in which these compounds are dissolved, and the compound (A) or the compound (B) is an aggregate as long as the viscosity is 100 mPa · s or less. -Includes those existing in a state where structures such as micelles and liquid crystals are formed or in a state where they are mixed. That is, the viscosity at 20 ° C. is 100 mPa
An aqueous composition containing the compound (A) or the compound (B) so as to be s or less.

The second aspect of the present invention relates to the above compound (A).
A slurry rheology modifier containing a compound (B) and a compound (B), wherein the compound (A) and the compound (B) are in the form of a reticulated aggregate in the aqueous solution when the aqueous solution S _A and the aqueous solution S _B are mixed. To a slurry rheology modifier capable of forming

The third aspect of the present invention relates to the above compound (A).
And a compound (B), which is a slurry rheology modifier, wherein the effective amount of the compound (A) and the effective amount of the compound (B) are 1 part by weight in total (wherein the effective amount of the compound (A) is Weight ratio of the effective component and the effective component of the compound (B) is (A) / (B)
= 5/95 to 95/5. ) And ordinary Portland cement 100 parts by weight and water 100 parts by weight at 20 ° C.
30 mL of the slurry of 500 mL in a 500 mL beaker
15 seconds ± 3 ml from the surface of water in 20 ml of water
A mechanical mixer (stirring blade type: anchor type, width × height = 68 mm ×) that fixed the distance from the lower end surface of the stirring blade to the inner bottom surface of the beaker to 1.5 cm after being charged for 5 seconds and allowed to stand for 10 seconds 68 mm) and 60 r.p.m. p.
m. The present invention relates to a slurry rheology modifier having an SS (suspended particle) concentration of 1000 mg / L or less in water sampled at a depth of 4.5 cm from the water surface after stirring for 10 seconds and standing for 10 seconds.

A fourth aspect of the present invention is a slurry rheology modifier containing the compound (A) and the compound (B), which is an effective component of the compound (A) and the compound (B).
5 parts by weight in total (in this total, the weight ratio of the active ingredient of the compound (A) to the active ingredient of the compound (B) is (A) /
(B) = 5/95 to 95/5. ) And 95 parts by weight of water at 20 ° C., the slurry rheology modifier satisfying the following characteristics. <Characteristics> Cone plate (diameter 50 mm, angle 0.03
98 rad, GAP0.0508mm) angular velocity ω is 1
~10rad / s minimum G _'min and a maximum value G' _max ratio G _'min / G' _max of storage modulus obtained in the range of 0.
It is 4-1.

The present invention also relates to a method for producing a slurry by adding the slurry rheology modifier of the present invention to a slurry.

In particular, the combination of the compound (A) and the compound (B) in the slurry rheology modifier of the present invention is
(1) A combination of a compound (A) selected from an amphoteric surfactant and a compound (B) selected from an anionic surfactant, (2) a compound (A) selected from a cationic surfactant and an anionic fragrance. When selected from the combination of the compound (B) selected from the group compounds, (3) the combination of the compound (A) selected from the cationic surfactant and the compound (B) selected from the brominated compound, So that the molar ratio of the effective components of the compound (A) and the compound (B) is preferably compound (A) / compound (B) = 1/20 to 20/1, and the compound (A) and the compound Provided is a method for producing a slurry to be added to a slurry such that the total effective content of (B) and the effective content in the aqueous phase of the slurry is preferably 0.01 to 20% by weight.

The present invention also prepares a slurry containing one compound of the compound (A) or the compound (B) of the slurry rheology modifier of the present invention, powder and water, and then adding the above slurry to the slurry. The present invention relates to a method for producing a slurry in which the other compound of the compound (A) or the compound (B) is added.

The slurry rheology modifier according to the present invention is a state in which a single molecule or a structure such as an associate, a micelle or a liquid crystal is formed in water in an aqueous solution containing the compound (A) or the compound (B) alone. In the mixed state, the aqueous solution has low viscosity, and the aqueous solution of the compound (A) and the compound (B)
The viscosity of the mixed solution can be greatly increased by mixing the aqueous solution of, the point of forming a network-like aggregate, the point of the SS concentration when the slurry is put into water within a specific range, or the specific storage elasticity. It is characterized by having a ratio. Therefore, the slurry rheology modifier according to the present invention exhibits a specific viscosity when the compound (A) and the compound (B) are combined, the formation of a network association, and the specific SS when the slurry is put into water. It is required that the compound has a concentration or a specific storage elastic modulus ratio, and the compound (A) or the compound (B) cannot be specified individually, and thus, "compound (A) and compound (B)" cannot be specified.
The above requirement is expressed by mixing and. " When the combination of the compound (A) and the compound (B) is specified, either one may be the compound (A). In the following, when one of the compounds is the compound (A),
The other is referred to as a compound (B) for convenience sake.

Aqueous solutions of the compound (A) and the compound (B), which are essential components of the slurry rheology modifier according to the present invention, have lower viscosities than an aqueous solution obtained by mixing the two, and a slurry rheology containing these compounds. By using the modifier, the operability of addition to the slurry system becomes extremely good.

When the slurry rheology modifier according to the present invention is added to the slurry system, the rheology of the slurry is modified and the aqueous phase of the slurry system thickens within a short time, resulting in the slurry system. The overall viscosity can be increased rapidly.

When the slurry relating to the combination of the compound (A) and the compound (B) is added, a string-like micelle, which is a higher-order structure of a so-called low-molecular compound, is formed in the aqueous phase of the slurry, and the string-like micelles are further formed. It is considered that the micelles form aggregates and the viscosity of the entire slurry increases. Further, the rheological properties of the cord-like micelles have a high viscoelasticity, and it is said that the cord-like micelle aggregates are entangled with each other in the aqueous phase in the slurry to form a three-dimensional mesh-like aggregate. Conceivable. By this feature, since the powder particles in the slurry of the present invention are covered with the mesh-like association of the highly viscoelastic string-like micelles, they are charged without being diluted even when water is present at the use site, Since it can be filled, for example, compared to conventional cement milk and mortar, the amount of slurry that diffuses in water is much less, and the surroundings of construction sites, groundwater,
It is possible to reduce the water pollution and the burden on drainage facilities in the downstream of the river. Moreover, since a network-like aggregate is formed by molecular association in the slurry, high viscosity can be imparted to the slurry. Since ordinary water-soluble polymers are connected by covalent bonds, the bond deteriorates when subjected to shearing force such as stirring, and eventually the bond breaks to lower molecular weight, whereas the network-like aggregates. Forms a large structure due to molecular association due to intermolecular force, so even if the aggregates are cut by shearing force, they can easily be recombined and re-fused to reconstruct the original shape. Conceivable. This feature is particularly effective for a slurry system in which powder particles, sand, gravel, etc. are present. For example, when the powder particles, sand, gravel, etc. are uniformly mixed, internal friction is generated, the aggregate is broken during injection and pumping, and the viscosity is significantly reduced. When the process is completed and the stress is released, an aggregate is formed again, so that an appropriate viscosity can be restored and material separation resistance can be imparted to the slurry.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The compound (A) and the compound (B) used for the slurry rheology modifier of the first aspect of the present invention are an aqueous solution S _A having a viscosity of the compound (A) of 100 mPa · s or less. When (B) is mixed with an aqueous solution S _B having a viscosity of 100 mPa · s or less, it is necessary that the viscosity be at least twice as high as that of any aqueous solution before mixing, and preferably at least 5 times, more preferably at least 10 times, more preferably at least 100 times, particularly preferably at least 5 times.
It is possible to increase it by 00 times. Here, the viscosity is measured with a B-type viscometer (C rotor [No. 3 rotor in the case of No. notation, 1.5 rpm to 12 rpm] at 20 ° C.). Say. in this case,
The viscosity behavior is 1.5 r.p.m. p. m. To 12r.
p. m. It may be expressed at any one of the rotation speeds. Less than,
Unless otherwise specified, viscosity means that measured under these conditions. Further, the mixing is carried out by mixing the respective aqueous solutions at a weight ratio of 50/50. Furthermore, from the viewpoint of operability when the slurry rheology modifier of the present invention is added to a slurry system, 20 ° C. of an aqueous solution of compound (A) and compound (B) before mixing.
It is desirable that the respective viscosity is 50 mPa · s or less, more preferably 10 mPa · s or less, and that a similar thickening effect is exhibited when the both liquids are mixed.
Further, the aqueous solution in which the compound (A) and the compound (B) are mixed should be in a state where a single molecule or a structure such as an aggregate, a micelle or a liquid crystal is formed in water or a mixture thereof at room temperature. Is preferred.

The concentrations of the compound (A) and the compound (B) are determined within a range in which the viscosity of the aqueous solution of the compound (A) and the compound (B) at 20 ° C. and the viscosity when the both are mixed satisfy the above requirements. It is possible to determine the preferable range when the compound (A) and the compound (B) are specified, but in consideration of the fact that the concentration range when added to the slurry can be widely selected, each is 0.01 ~ 5
It is preferable to select the compound (A) and the compound (B) whose concentration can be determined in the range of 0% by weight.

The slurry rheology modifier of the present invention imparts good rheological properties even in a slurry system having a high ionic strength. Therefore, an aqueous solution obtained by mixing the aqueous solution S _A and the aqueous solution S _B has an electric conductivity of 0. 1-80mS / c
m, preferably 0.1 to 60 mS / cm, particularly preferably 1 to 40 mS / cm, it is desired to exhibit the above viscosity behavior.

Further, the slurry rheology modifier of the present invention imparts good rheological properties even in a slurry system having high ionic strength. Therefore, the aqueous solution obtained by mixing the aqueous solution S _A and the aqueous solution S _B is the compound (A), the compound It contains at least one compound different from (B) and has an electric conductivity at 20 ° C. of 0.1 to 80 mS / cm, preferably 0.1 to 20 mS / cm.
It is desired that the above viscosity behavior is exhibited even at 60 mS / cm, particularly preferably 1 to 40 mS / cm.
Examples of such a compound include an electrolyte, and examples of ionizing ions include cations such as potassium ion, sodium ion, iron ion, and aluminum ion, and anions such as hydroxy ion, sulfate ion, and chloride ion.

In the second aspect of the present invention, it is necessary that the compound (A) and the compound (B) form a network association in an aqueous solution obtained by mixing the aqueous solution S _A and the aqueous solution S _B. The mesh-like aggregates referred to herein include a three-dimensional mesh structure, a net or network structure, a sponge (sponge) structure, a fiber (fiber) structure, a branched structure and the like. This mesh-like aggregate was determined under a scanning electron microscope, and is shown in FIG.
As shown in Fig. 2, the string-like aggregates are entangled to form a mesh. The length between the intersections of the string-like aggregates forming the mesh is preferably 0.01 to 100 μm,
0.05 to 10 μm is particularly preferable. The diameter of the string-like aggregates forming the mesh is 0.01 to 2 μm, especially 0.0
5 to 0.5 μm is preferable. For the observation with a scanning electron microscope, an aqueous solution containing the compound (A) and the compound (B) is instantaneously frozen and observed.

The contents of the compound (A) and the compound (B) capable of forming a network-like aggregate can be selected in the aqueous solution S _A or the aqueous solution S _B in consideration of the fact that the concentration when added to the slurry can be widely selected. , 0.01 to 50% by weight is preferable, and 0.01 to 30% by weight is particularly preferable. In the second aspect of the present invention, compound (A) and compound (B)
Can use the compound (A) and the compound (B) of the first aspect.

In observation with a scanning electron microscope, 0.01
It is preferable to select from a magnifying power with which an object of ˜100 μm can be confirmed, and specifically, 100 to 10,000 times is preferable. For the length and diameter between the intersections, the observation image is photographed (or a hard copy of the image), and the length between the intersections of the string-like portions forming the mesh-like aggregate on the photograph is measured using a standard scale. To measure. The diameter is the length measured in the direction (width) orthogonal to the longitudinal direction of the part that looks like the string, using a standard scale.

In the third aspect of the present invention, it is necessary that when the slurry containing the compound (A) and the compound (B) is put into water, the slurry does not scatter in water. In the third aspect of the present invention, compound (A) and compound (B)
Can use the compound (A) and the compound (B) of the first aspect. The method of measuring the degree of dispersion is performed as follows.

A total of 1 part by weight of the active ingredient of the compound (A) and the active ingredient of the compound (B) (in this total, the weight ratio of the compound (A) and the compound (B) is (A) / (B)). = 5 / 95-9
It is 5/5. ) And ordinary Portland cement 100 parts by weight and water 100 parts by weight at 30 ° C. Slurry 30
Within 1 minute after preparing the slurry, 500 mL of water at 20 ° C. in a 500 mL beaker (diameter: 85 mm, height: 120 mm) was charged from a position of 3 cm from the water surface for 15 seconds ± 5 seconds, and allowed to stand for 10 seconds. After that, a mechanical mixer in which the distance from the lower end surface of the stirring blade to the inner bottom surface of the beaker is fixed to 1.5 cm (stirring blade type: anchor type, width ×
Height = 68 mm × 68 mm), 60 r.p.m. p. m. In 1
3. Stir for 0 seconds, leave still for 10 seconds, and then set to a depth of 4.
The SS (suspended particle) concentration in the water sampled at a position of 5 cm is measured. SS concentration is 1000 mg / L or less, 5
00 mg / L or less is preferable, and 350 mg / L or less is particularly preferable. The slurry is prepared within 2 minutes.
In addition, the specific method of measuring the SS concentration in the collected water is
This is shown in the examples below. Further, a schematic view of the stirring blade housed in the beaker is shown in FIG. In FIG. 2, 1 is a stirring blade, 2 is a 500 ml beaker, and the distance between the lower end surface 1 ′ of the stirring blade and the inner bottom surface 2 ′ of the beaker is 15 mm.

In the third embodiment, the water collected as described above has a turbidity of 30 after satisfying the SS concentration.
% Or less, more preferably 6% or less. Turbidity is
Within one minute after collecting the collected water, use a turbidimeter [colorimetric color difference meter (Mo
del ND-1001DP, manufactured by Nippon Denshoku Industries Co., Ltd., absorption cell length 10 mm, 12V50W halogen lamp)]. Turbidity can be an indicator of dispersion along with SS concentration.

In the third embodiment, in the above-mentioned slurry used for measuring SS and turbidity, the weight ratio of compound (A) and compound (B) is an effective component, and (A) / (B) = 5. / 9
It can be arbitrarily selected within the range of 5 to 95/5. This means that in the total of the compound (A) and the compound (B), each of the compound (A) and the compound (B) accounts for at least 5% by weight as an effective component.

In the fourth aspect of the present invention, it is necessary that the aqueous solution containing the compound (A) and the compound (B) has specific rheological properties. This rheological property is
A total of 5 effective doses of compound (A) and compound (B)
20 parts by weight consisting of parts by weight (in this total, the weight ratio of compound (A) and compound (B) is (A) / (B) = 5/95 to 95/5) and 95 parts by weight of water. Concerning the aqueous solution, a cone plate (diameter 50 mm, angle 0.0398 rad, GAP0 ..) was measured with a viscoelasticity measuring device (ARES viscoelasticity measuring device, manufactured by Rheometric Scientific).
0508 mm) and the angular velocity ω is 1 to 10 rad / s
'Measured, G obtained in the range of the omega' in the storage modulus G ratio ranges G _'min of the minimum value G' _min and a maximum value G _'max of
/ G ' _max is in the range of 0.4 to 1. G ' _min
/ G ' _max = 0.5 to 1 is more preferable, and 0.7 to 1 is particularly preferable. Also, G _'min is 1 to 1000, further 2
500, particularly preferably in the range of 4 to 100, G _'max is 2 to 1000, further from 5 to 500, particularly 1
It is preferably in the range of 0 to 100.

In the fourth embodiment, the weight ratio of the effective components of the compound (A) and the compound (B) is (A) / (B) = 5 /
It can be arbitrarily selected within the range of 95 to 95/5.
This means that in the total of the compound (A) and the compound (B), each of the compound (A) and the compound (B) accounts for at least 5% by weight as an effective component. In a fourth aspect of the present invention, the compound (A) and the compound (B) are the above-mentioned first
The compound (A) and the compound (B) of the embodiment can be used.

The compounds (A) and (B) according to the first to fourth aspects of the present invention may be combined in any manner as long as they satisfy the behavior specified in the present invention. From the viewpoint of the stability of the dispersibility of the slurry system, the compound (A) and the compound (B) each have a molecular weight (the formula weight in the case of an inorganic compound) of 1000 or less, preferably 700.
Or less, more preferably 500 or less, and in the case of a polymer, the weight average molecular weight (for example, gel permeation chromatography / polyethylene oxide conversion) is 50.
Less than 0, preferably 400 or less, more preferably 300
The following is desired. In addition, a mixed solution of an aqueous solution of the compound (A) and an aqueous solution of the compound (B) at room temperature
It is preferable that phase separation from water does not occur in a state in which a single molecule or a structure such as an aggregate, a micelle, a liquid crystal or the like is formed in water or a mixture thereof.

Compound (A) and compound (B) of the present invention
Satisfies the requirement of the first aspect, and further,
To those satisfying one or more requirements selected from the requirements defined in the aspects of (4) to (4), and further preferably satisfying two or more requirements, especially three requirements.

The slurry rheology modifier according to the present invention may be any combination of the compound (A) and the compound (B) as long as they exhibit the above-mentioned behavior. (A) and compound (B)
The combination of (1) a compound (A) selected from an amphoteric surfactant and a compound (B) selected from an anionic surfactant, and (2) a compound (A) selected from a cationic surfactant. ) And an anionic aromatic compound (B)
And (3) a combination of a compound (A) selected from a cationic surfactant and a compound (B) selected from a brominated compound.

As those selected from the amphoteric surfactants,
Betaine-type amphoteric surfactants are preferable, and dodecanoic acid amidopropyl betaine, octadecanoic acid amidopropyl betaine, dodecyldimethylaminoacetic acid betaine, and the like are mentioned, and from the viewpoint of viscosity expression, dodecanoic acid amidopropyl betaine is preferable.

As those selected from the anionic surfactants, ethylene oxide addition type alkyl sulfate ester type surfactants are preferable, and POE (3) dodecyl ether sulfate ester salt, POE (2) dodecyl ether sulfate ester salt, POE. (4) Dodecyl ether sulfate ester salt and the like, and examples of the salt include metal salts such as sodium salt and alkanolamine salts such as triethanolamine salt.

Among these, dodecanoic acid amidopropyl betaine and POE (3) dodecyl ether sulfate ester triethanolamine or POE (, which exerts an effect even when the solid content (effective content) concentration in the aqueous phase of the slurry is 20% by weight or less, 3) A combination of sodium dodecyl ether sulfate is preferable. POE is an abbreviation for polyoxyethylene, and the number in () is the average number of moles of ethylene oxide added (the same applies hereinafter).

As the one selected from the cationic surfactants, a quaternary salt type cationic surfactant is preferable, and as the quaternary salt type cationic surfactant, 10 in the structure is included.
Those having at least one saturated or unsaturated straight-chain or branched-chain alkyl group containing from 26 to 26 carbon atoms are preferred. For example, alkyl (10 to 26 carbon atoms) trimethylammonium salt, alkyl (10 to 26 carbon atoms)
Examples thereof include pyridinium salts, alkyl (C10-26) imidazolinium salts, alkyl (C10-26) dimethylbenzylammonium salts, and specifically, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, Octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, tallowtrimethylammonium chloride, tallowtrimethylammonium bromide, hydrogenated tallowtrimethylammonium chloride, hydrogenated tallowtrimethylammonium bromide, hexadecylethyldimethylammonium chloride, octadecylethyldimethylammonium chloride, hexadecylpropyl Dimethylammonium chloride, hexadecyl Pyridinium chloride, 1,1
Examples thereof include dimethyl-2-hexadecylimidazolinium chloride and hexadecyldimethylbenzylammonium chloride. These may be used in combination of two or more.
From the viewpoint of water solubility and thickening effect, specifically, hexadecyltrimethylammonium chloride (for example, Coatamine 60W manufactured by Kao Corporation), octadecyltrimethylammonium chloride, hexadecylpyridinium chloride and the like are preferable. From the viewpoint of temperature stability of thickening effect, it is preferable to use two or more kinds of the above-mentioned cationic surfactants having different alkyl group carbon numbers as one of the compound (A) and the compound (B).

In particular, when the slurry rheology modifier of the present invention is applied to concrete or the like, it is preferable to use a quaternary ammonium salt containing no halogen such as chlorine from the viewpoint of preventing corrosion of reinforcing bars and deterioration of concrete due to salt damage. preferable.

Examples of quaternary salts containing no halogen such as chlorine include ammonium salts and imidazolinium salts. Specific examples include hexadecyltrimethylammonium methosulfate, hexadecyldimethylethylammonium ethosulfate and octadecyltrimethylammonium methoxide. Sulfate, octadecyldimethylethylammonium ethosulfate, tallowtrimethylammonium methosulfate, tallowdimethylethylammonium ethosulfate, 1,1-dimethyl-2-hexadecylimidazolinium methosulfate, hexadecyldimethylhydroxyethylammonium acetate, octadecyldimethylhydroxyethyl Ammonium acetate, hexadecyl dimethyl hydroxyethyl ammonium propio Over DOO, octadecyl dimethyl hydroxyethyl ammonium propionate, tallow dimethyl hydroxyethyl ammonium acetate, tallow dimethyl hydroxyethyl ammonium propionate, and the like. A quaternary ammonium salt containing no halogen such as chlorine can be obtained, for example, by quaternizing a tertiary amine with dimethylsulfate or diethylsulfate.

Examples of compounds 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, and specifically, salicylic acid and p-toluene sulfone. 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, which may form a salt, may be used in combination of two or more kinds. However, in the case of a polymer, the weight average molecular weight (for example, gel permeation chromatography / polyethylene oxide conversion) is preferably less than 500.

As the compound selected from the bromide compounds, an inorganic salt is preferable, and NaBr, KBr, HBr and the like can be mentioned.

In the present invention, the compound (A) and the compound (B) are likely to form an association product, but each has a low viscosity even in a concentrated aqueous solution, and is a rheology modifier in the aqueous phase of the slurry. Even if the effective component concentration is low, an excellent slurry rheology modifying effect is exhibited, and even a concentrated aqueous solution has low viscosity, which is preferable from the viewpoint of workability at the time of addition.
In the present invention, thickening of the slurry can be achieved with an extremely low addition amount of the effective component concentration of 10% by weight or less.
Even in a slurry system with high ionic strength, the same effect can be exhibited, and depending on the slurry system, the resistance to material separation is very stable, especially when contacted with the aqueous phase. The compound (A) is selected from the quaternary ammonium salt type cationic surfactants, and the compound (B) is an anionic aromatic compound or bromide, in order to develop rheological properties that could not be obtained with the above. Especially preferred are combinations which are selected from compounds. This is especially useful for slurries containing hydraulic powders.

Further, the compound (A) is alkyl (having 1 carbon atom).
0 to 26) trimethylammonium salt, and the combination in which the compound (B) is a sulfonate having an aromatic ring is particularly preferable, and the effect is exhibited even when the effective component concentration in the aqueous phase of the slurry is 5% by weight or less. In particular, when it is used in a slurry of hydraulic powder, among these, toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, styrene sulfonic acid or salts thereof are used as the compound (B) from the viewpoint of causing no curing delay. Particularly preferred is p-toluenesulfonic acid or a salt thereof.

The reason why the characteristic slurry rheological properties are obtained by using the compound (A) and the compound (B) together as the slurry rheology modifier according to the present invention is considered to be as follows.

When the compound (A) and the compound (B) are mixed, an aggregate can be formed in the aqueous phase in a short time and viscosity can be efficiently imparted. It is considered that since the uniform water content is used to completely supplement the excess water content, by suppressing the breathing water with time, it is possible to obtain the property of excellent material separation resistance even in the case of a slurry composition having a large amount of unit water.

The compound (A) and the compound (B), even if they are low molecular weight compounds, form a large polymer network-like association by causing a molecular association in the slurry, so that a high viscosity is imparted to the slurry. It is thought that it can be done.

Furthermore, since the powder particles in the slurry containing the compound (A) and the compound (B) are covered with the highly viscoelastic network-like aggregate, they are diluted even when water is present at the site of use. It can be charged and filled without water pollution.

In particular, when the slurry rheology modifier of the present invention relating to a combination of a quaternary ammonium salt type cationic surfactant and a compound selected from anionic aromatic compounds or brominated compounds is used, It is considered that finely branched aggregates are formed in the aqueous phase.

Further, since ordinary water-soluble polymers are connected by covalent bonds, the bond deteriorates when subjected to repeated shearing force, and eventually the bond is broken to lower the molecular weight. It is considered that when the aqueous phase receives a strong stress, the aggregate structure is destroyed, so that excessive stress is suppressed, and when the stress decreases, the aggregate is formed again. This is characterized by imparting an appropriate viscosity to the slurry.

Taking advantage of such characteristics, it is particularly effective in the case of a slurry system in which powder particles, sand, gravel, etc. exist.
Even when the slurry is strongly sheared by stirring, pouring, and pressure-feeding, the aggregate re-forms when released from the shear, so that high shear resistance can be imparted to the slurry. For example, it is possible to produce or transport the slurry while suppressing the occurrence of excessive internal friction, and to impart appropriate viscosity to the slurry after the production or transportation.

Further, since the powder particles in the slurry containing the compound (A) and the compound (B) are covered with the network-like aggregate having high viscoelasticity, they are diluted even when water is present at the site of use. It can be charged and filled without water pollution.

When compound (A) selected from amphoteric surfactants, compound (B) selected from anionic surfactants, or compound (A) selected from cationic surfactants. When a compound (B) selected from an anionic aromatic compound or a compound selected from a bromide compound is used as the compound (B), the viscosity is low even in a concentrated aqueous solution of each compound alone, and therefore the compound is added to the slurry system. The effective concentration of the previous aqueous solution is preferably 10
By setting the amount to be not less than 20% by weight, more preferably not less than 20% by weight, further preferably not less than 30% by weight, and most preferably not less than 40% by weight, it is possible to improve the productivity such as downsizing of the storage tank.

In the slurry rheology modifier according to the present invention, other components such as a dispersant, an AE agent, a retarder, an early strengthening agent, an accelerator and a foaming agent can be used as long as the performance of the present modifier is not hindered. , A foaming agent, an antifoaming agent, an antirust agent, a colorant, an antifungal agent, a crack reducing agent, a swelling agent, a dye, a pigment and the like.

Since the slurry having a modified rheology can be obtained by adding the compound (A) and the compound (B) to the slurry, the addition form of the slurry rheology modifier according to the present invention is not particularly limited. The preferred method of using the slurry rheology modifier of the present invention is described below.

The slurry rheology modifier according to the present invention exhibits a large viscosity when mixed even if the compound (A) and the compound (B) are in the form of an extremely low-viscosity aqueous solution. Therefore, from the viewpoint of operability. , When added to the slurry system, each at 100 at the temperature used.
It is preferably used in the state of an aqueous solution having a viscosity of mPa · s or less, preferably 50 mPa · s or less, more preferably 10 mPa · s or less.

In the present invention, two kinds of compounds in which the aqueous solution exhibits a specific viscosity behavior, two kinds of compounds forming a network-like aggregate, and the SS concentration when the slurry is put in water are within a specific range 2. Two compounds are used as rheology modifiers for slurries, with one compound or an aqueous solution falling within a specific storage modulus ratio range. When these two kinds of compounds are a compound (A) and a compound (B), the present invention provides a method for modifying the rheology of a slurry by adding the compound (A) and the compound (B) to the slurry. In that case, one of the compound (A) and the compound (B) can be added to the slurry, and the other compound can be added to the slurry.

Further, since the compound (A) or the compound (B) can be mixed in the slurry in any order, one compound is added to the slurry at an appropriate stage, and the slurry is added to the slurry at a stage where viscosity is required. From the viewpoint of workability, it is preferable to add the other. The state of the compound (A) or the compound (B) when added may be liquid or powder.

The slurry rheology modifier of the present invention is a combination of one selected from a cationic surfactant and one selected from an anionic aromatic compound or a bromide compound, and a hydraulic powder such as cement is used. When used in a slurry system, the hydration reaction of the cement particles can be controlled, from the viewpoint of suppressing entrained bubbles during slurry stirring,
It is preferred to add the anionic aromatic compound or bromide compound to the slurry first and then add the cationic surfactant.

The slurry rheology modifier of the present invention can be specified by the expression of a specific viscous behavior, the formation of a network-like aggregate, the SS concentration when the slurry is put into water, or the specific storage elastic modulus ratio. When each of the compound (A) and the compound (B) is not a mixture derived from a natural product (for example, a compound derived from beef tallow) but a single compound, the association between the compound (A) and the compound (B) From the viewpoint of efficiently forming a coalescence, it is preferable to define the molar ratio and mix them.

In the slurry rheology modifier of the present invention, the molar ratio of the compound (A) and the compound (B) (effective component molar ratio) depends on the combination of the compound (A) and the compound (B) to increase the thickening effect. The high region is different and may be appropriately determined depending on the intended degree of thickening. Particularly, the combination of the compound (A) and the compound (B) is (1) a compound (A) selected from amphoteric surfactants. And a combination of a compound (B) selected from an anionic surfactant, (2) a combination of a compound (A) selected from a cationic surfactant and a compound (B) selected from an anionic aromatic compound, 3)
When selected from a combination of a compound (A) selected from a cationic surfactant and a compound (B) selected from a brominated compound, the compound (A) / Compound (B) = 1/20 to 20 /
1, preferably 1/20 to 4/1, more preferably 1 /
3 to 2/1 and particularly preferably 1/1 to 2/3 are suitable.

Furthermore, since the slurry rheology modifier of the present invention can impart good rheological properties even in a slurry system having high ionic strength, the electrical conductivity of the aqueous phase is 0.01.
In the range of -80 mS / cm, preferably 0.1-60 mS
/ Cm, particularly preferably 1 to 40 mS / cm for use in slurries. In particular, it is preferably applied to a slurry system containing a hydraulic composition such as cement and having a high electric conductivity in an aqueous phase.

According to the present invention, a slurry containing the slurry rheology modifier of the present invention, particularly a slurry containing the slurry rheology modifier of the present invention, hydraulic powder, and water is obtained. be able to.

The compound (A) and the compound (B) in the present invention may be used in the form of either an aqueous solution or a powder. In particular, the slurry rheology modifier of the present invention may have good slurry rheological properties in either form. Can be given. If the compound (A) and the compound (B) are used in the form of powder in advance, workability in premix applications and the like will be good. However, considering that the slurry can be adjusted to a desired viscosity, the compound (A)
It is preferable that the compound (B) and the compound (B) are not surface-treated in advance with a filler which is a constituent powder of the slurry.

The slurry rheology modifier of the present invention can be preferably applied to a slurry having a water powder ratio of 30 to 300%. As the powder for producing this slurry, a hydraulic powder having physical properties of being hardened by a hydration reaction can be used. Examples include cement and gypsum. Also,
Fillers can also be used, such as calcium carbonate,
Examples thereof include fly ash, blast furnace slag, silica fume, bentonite, and clay (natural minerals containing hydrous aluminum silicate as a main component: kaolinite, halosite, etc.). These powders may be used alone or as a mixture. Furthermore, sand or gravel as an aggregate and a mixture thereof may be added to these powders as needed. Also,
It can also be applied to a slurry of inorganic oxide-based powder other than the above, such as titanium oxide, or soil.

Further, the compound (A) and /
Alternatively, compound (B) and hydraulic powder can be premixed to prepare a hydraulic powder composition containing the slurry rheology modifier of the present invention.

In the slurry rheology modifier of the present invention, the effective component concentrations of the compound (A) and the compound (B) in the slurry may be appropriately determined according to the desired degree of thickening. The slurry rheology modifier of the present invention,
A slurry containing the modifier of the present invention can be obtained by a method such as addition to a slurry prepared in advance or addition at the time of producing the slurry. In particular, a slurry containing one of the compound (A) or the compound (B) and a powder, for example, a hydraulic powder such as cement and water is prepared, and then the compound (A) or the compound (B) is added to the slurry. The method of adding the other compound of 1) is preferable from the viewpoint of workability. The combination of the compound (A) and the compound (B) is (1) the combination of the compound (A) selected from the amphoteric surfactant and the compound (B) selected from the anionic surfactant, and (2) A combination of a compound (A) selected from a cationic surfactant and a compound (B) selected from an anionic aromatic compound, (3) a compound (A) selected from a cationic surfactant and a brominated compound. When the combination of the compound (B) is selected from the following, the total effective amount of the compound (A) and the compound (B) is 0.01 to 20% by weight in terms of the effective concentration in the aqueous phase of the slurry. , 0.1 to 15% by weight,
0.1 to 10% by weight, especially 0.3 to 10% by weight
It is preferable to use so that

The hydraulic slurry containing the slurry rheology modifier of the present invention may contain a dispersant. The dispersant is a lignin sulfonate and its derivative as a water reducing agent, an oxycarboxylic acid salt, a polyol derivative, a high-performance water reducing agent and a high-performance AE water reducing agent as a naphthalene type (Kao Corporation: Mighty 150), a melamine type. (Kao Corporation
Made: Mighty 150V-2), polycarboxylic acid type (Kao Co., Ltd .: Mighty 3000, NMB: Rheobuild SP, Nippon Shokubai: Aqualock FC600, Aqualock FC900), polycarboxylic acid as an anion activator. Acid type surfactant (Koi Co., Ltd .: Poise series)
Etc. Among them, the polycarboxylic acid type high-performance water reducing agent and the polycarboxylic acid type surfactant are preferable in that both the fluidity and the viscosity of the slurry can be achieved.

The content of the dispersant in the hydraulic slurry containing the slurry rheology modifier of the present invention is generally 0.01 to 5% by weight, more preferably 0.05 to 3% by weight of the active ingredient based on the hydraulic powder. Weight percent is preferred.

The compound (A) and the compound (B) of the present invention can be used in combination with other existing thickeners. Other existing thickeners include, for example, cellulose derivatives, polyacrylic polymers, polyethylene oxide, polyvinyl alcohol, gum polysaccharides, microbial fermentation polysaccharides and the like.

The hydraulic slurry containing the slurry rheology modifier of the present invention contains other components such as an AE agent, a retarder, an early strengthening agent, an accelerator, a foaming agent, as long as the performance of the agent is not impaired. It may contain a foaming agent, an antifoaming agent, a crack reducing agent, an expanding agent and the like.

The cured composition obtained by curing the slurry containing the slurry rheology modifier of the present invention and the hydraulic powder has excellent initial cured physical properties. Further, an aggregate can be mixed with a hydraulic slurry containing the slurry rheology modifier of the present invention to prepare a hydraulic composition. A cured composition obtained by curing this hydraulic composition has excellent initial cured physical properties, and is particularly preferably used for structures and the like.

Fine aggregates and coarse aggregates may be used as the aggregates to be mixed with the hydraulic slurry containing the slurry rheology modifier of the present invention. A material having a high material strength is preferable. Coarse aggregates include rivers, land, mountains, sea, lime gravel, crushed stones of these, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural) and recycled coarse aggregate. Can be mentioned. Fine aggregates include river, land, mountain, sea, lime sand, silica sand and crushed sand thereof, blast furnace slag fine aggregate, ferronickel slag fine aggregate, lightweight fine aggregate (artificial and natural) and recycled fine aggregate. Etc.

[0080]

Examples Example 1 (1) Using the compounds (A) and (B) shown in Table 1, 2
Aqueous solutions were prepared in which the solid content concentrations were adjusted so that the viscosities at 0 ° C were the values shown in Table 2, and were designated as aqueous solution A and aqueous solution B, respectively. The compounds of Table 1 were also used in the following Examples and Comparative Examples. An aqueous solution for evaluation was prepared from the compounds of Table 1 at the concentrations shown in Table 1, and the density of the aqueous solution was measured. The results are also shown in Table 1. From the relationship between the aqueous solution concentration and the aqueous solution density, the density of the aqueous solution prepared in this example (Table 2) was
Both were 1.0 (g / cm ³ ).

(2) Aqueous solutions A and B prepared in (1)
For each of the combinations in Table 2, 100 ml (100
g) A mixture (A + B) was prepared by mixing and stirring for 10 seconds with a stirrer with a stirring blade, and the viscosity at 20 ° C. was measured. The results are shown in Table 2. The viscosity is measured by a B-type viscometer (Tokyo Keiki, DVM-B, C rotor, 1.5 rp.
m to 12r. p. m) was used for the measurement. The conductivity is HORIBA CONDUCTIVITY ME
It was measured using TER DS-15.

(3) In Comparative Examples 1 to 3, comparison was made so that the viscosity was about the same as the viscosity of the mixed liquid (A + B) of the examples in Table 2 when diluted with an equal amount of water (alternative to the aqueous solution B). Items 1-3
An aqueous solution in which the solid content concentration of was adjusted was prepared and designated as aqueous solution A.

[0083]

[Table 1]

[0084]

[Table 2]

(Note) The conductivity of the mixed solution (A + B) at 20 ° C. is as shown in Examples 1-1, 1-2, 1-3, 1-5, 1
-6, 1-7, 1-9, 1-10, 1-11 are 2-8m
S / cm, Examples 1-4 and 1-8 are 26-40 mS / c
It was m.

Example 2 The same measurement as in Example 1 was carried out using an aqueous solution B in which sodium hydroxide was dissolved at a concentration of 0.6% by weight as shown in Table 3. The results are shown in Table 3.

[0087]

[Table 3]

(Note) Examples 2-1 to 2-9 and Comparative Example 2
The solid content concentration of the aqueous solution (B) in -4 to 2-5 is the total concentration of 0.6% by weight of sodium hydroxide and the amount of the compound (B).

The electric conductivity of the mixed solution (A + B) at 20 ° C. was measured in Examples 2-1, 2-2, 2-3, 2-5, 2
-6, 2-7, 2-8, 2-9, 2-10, 2-12,
2-13 and 2-14 are 32 to 38 mS / cm, Example 2
-4 and 2-11 are 56 to 70 mS / cm, Comparative Example 2-1.
˜2-5 was 30 to 34 mS / cm.

Examples 3 to 13 and Comparative Examples 3 to 5, 10,
13 (1) Slurry formulation A slurry having the composition shown in Table 4 was prepared. Formulation I was used in Example 3 and Comparative Example 3 (Table 5). Similarly, the formulations II to XI are those of Example 4, Comparative Example 4 (Table 6) to Example 13, and Comparative Example 13.
Used in (Table 15).

[0091]

[Table 4]

(2) Preparation of Slurry Examples and Comparative Examples 3-5, 3-6, 4-8, 4-9, 5-
5, 5-6, 10-5, 10-6, 13-5, 13-6
For, the fine powder, water and the compound (B) were previously kneaded for 30 seconds, and then the compound (A) was added and kneaded until the fluidity remained unchanged.

In other comparative examples, the fine powder and water were previously kneaded for 30 seconds, and then the compound of the comparative product was added and kneaded until the fluidity remained unchanged. In the following, the same operation as in the example was performed.

The kneading was carried out by using a homomixer for Formulation I,
For other formulations, a mortar mixer was used. The slurry was prepared at 20 ° C. After slurry preparation, kneading time shown below, slurry flow value, slurry viscosity,
Five types of evaluation items, that is, separation resistance in water and the amount of breathing water were measured. The hydration rates of the formulations II, III, and XI (Tables 6, 7, and 15) were also measured.

(3) Evaluation (3-1) Slurry flow value The prepared slurry was packed in a cylindrical cone having a height of 45 mm and an inner diameter of 45 mm, and then gently pulled up vertically. The diameter (mm) of the slurry at the time when it was completely spread was measured.

(3-2) Kneading time A slurry of fine powder such as cement and water alone loses fluidity due to addition of the compound (A) or a comparative thickener, and fluidity does not change even after stirring. The time point was judged visually (visually). The evaluation criteria are shown below. ◎ Within 5 seconds ○ Over 5 seconds within 10 seconds △ Over 10 seconds within 30 seconds × Over 30 seconds within 2 minutes

(3-3) Slurry Viscosity (Pa · s) The prepared slurry was used for the outer cylinder φ27 mm, the inner cylinder φ14 mm,
A sample container was filled with a sample height of 65 mm, and an inner cylindrical rotary rheometer (Mettler RM260 Rheo manufactured by METTLER CORPORATION) was used.
mater) (outer cylinder diameter 27 mm, inner cylinder diameter 25 m
m, sample height 65 mm), shear rate of inner cylinder is 30 sec
^{-Exponentially} increase to ^{-1 in} 30 seconds, shear rate 0.5 ~
Bingham approximation was performed at 3.0 sec ^-1 , and the viscosity at 20 ° C was measured.

(3-4) Separation resistance in water 10 g of the prepared slurry was measured and 400 ml of tap water
Gently settle in a 500 ml beaker containing. The state in which the slurry floated up in water was visually evaluated (visually). The evaluation criteria are shown below. ◎ The water phase is completely transparent, and the whole settled slurry can be confirmed. ○ The entire slurry that settled to the bottom can be confirmed. Δ The water phase becomes cloudy, but part of the slurry that settled at the bottom of the beaker is visible. × The water phase becomes cloudy and the bottom of the beaker cannot be seen.

(3-5) Breathing water amount 200 g of the prepared slurry was put in a 500 ml beaker,
After standing still for 30 minutes, the breathing water appearing on the surface was sucked up with a dropper and weighed. The evaluation criteria are shown below. ◎ Breathing water amount 0 g (none) ○ Breathing water amount over 0 g and 1 g or less △ Breathing water amount over 1 g and 5 g or less × Breathing water amount over 5 g The results are shown in Tables 5 to 15. In addition, the addition amount in Tables 5 to 15 is the total effective component concentration (% by weight) of the compound (A) and the compound (B) in the aqueous phase of the slurry having the formulation of Table 4.

(3-6) Hydration rate 20 g of the prepared slurry was added to a calorimeter (TOKY
Made by Oriko Co, TWIN CONDUCTIO
N MICRO CALORIMETER Model
TCC-2-6), and the second hydration exothermic peak time was measured. The evaluation criteria are shown below. The results are shown in Table 6,
7 and 15 are also shown. ◎ More than 5 hours and less than 15 hours ○ More than 15 hours and less than 25 hours △ More than 25 hours and less than 35 hours × more than 35 hours

[0101]

[Table 5]

Note: Table 5 shows the results using Slurry Formulation I.

Comparative Examples 3-1, 3-5, and 3-6 do not exhibit thickening properties, so that the slurry has no separation resistance and the slurry flow value becomes large.

In addition, 20% of slurry containing each compound was added.
The electrical conductivity at 0 ° C. is 2 to 10 in all Examples and Comparative Examples.
It was mS / cm.

[0105]

[Table 6]

Note: Table 6 shows the results using Slurry Formulation II.

Since Comparative Examples 4-1, 4-8, and 4-9 do not exhibit thickening, the slurry has no separation resistance and the slurry flow value becomes large.

In addition, 20% of slurry containing each compound was added.
The electrical conductivity at 25 ° C. is 25 to 3 in all Examples and Comparative Examples.
It was 3 mS / cm.

[0109]

[Table 7]

(Note) Table 7 shows the results obtained by using the slurry formulation III.

Comparative Examples 5-1, 5-5, and 5-6 do not exhibit thickening properties, so that the slurry has no separation resistance and the slurry flow value becomes large.

Further, 20% of slurry containing each compound was added.
The electrical conductivity at ℃ is 35 to 4 in all Examples and Comparative Examples.
It was 0 mS / cm.

[0113]

[Table 8]

Note: Table 8 shows the results using Slurry Formulation IV.

The conductivity at 20 ° C. of the slurries containing the respective compounds was 2.5 to 3.5 mS / c in all the examples.
It was m.

[0116]

[Table 9]

(Note) Table 9 shows the results obtained by using the slurry formulation V.

The electrical conductivity of the slurry containing each compound at 20 ° C. was 3.8 to 4.5 mS / c in all the examples.
It was m.

[0119]

[Table 10]

(Note) Table 10 shows the results obtained by using the slurry formulation VI.

The electrical conductivity of the slurry containing each compound at 20 ° C. was 0.1 to 0.2 mS / c in all the examples.
It was m.

[0122]

[Table 11]

Note: Table 11 shows the results using Slurry Formulation VII.

The electrical conductivity at 20 ° C. of the slurries containing each compound was 4.5 to 5 mS / cm in all the examples.

[0125]

[Table 12]

(Note) Table 12 shows the results using Slurry Formulation VIII.

Comparative Examples 10-1, 10-5, 10-6 are
Since it does not exhibit thickening, the slurry has no separation resistance,
The slurry flow value increases.

In addition, 20% of slurry containing each compound was added.
The electrical conductivity at ℃ is 1 to 2 m in all Examples and Comparative Examples.
It was S / cm.

[0129]

[Table 13]

Note: Table 13 shows the results using Slurry Formulation IX.

The electrical conductivity of the slurry containing each compound at 20 ° C. was 0.5 to 2 mS / cm in all the examples.

[0132]

[Table 14]

(Note) Table 14 shows the results using the slurry formulation X.

The electrical conductivity of the slurry containing each compound at 20 ° C. was 0.5 to 2 mS / cm in all the examples.

[0135]

[Table 15]

Note: Table 15 shows the results using Slurry Formulation XI.

Comparative Examples 13-1, 13-5 and 13-6 are
Since it does not exhibit thickening, the slurry has no separation resistance,
The slurry flow value increases.

In addition, 20% of slurry containing each compound was added.
The electrical conductivity at C is 6 to 8 m in all the examples and comparative examples.
It was S / cm.

From Example 1, in the compounds (A) and (B) of the present invention, the viscosity of the aqueous solution after mixing increases from 10 times to 100 times or more as compared with the viscosity of each aqueous solution before mixing. I understand. In particular, when the compound (A) is selected from quaternary ammonium salt type cationic surfactants and the compound (B) is selected from an anionic aromatic compound or a brominated compound, before mixing Aqueous solution with low viscosity of 10 mPa · s or less and 10% by weight
Even at the following low concentrations, the viscosity after mixing increased 500 times or more.

On the other hand, in Comparative Example 1 relating to the conventional thickener, in order to obtain the same viscosity as that of Example 1 after mixing, the viscosity before mixing must be set to be extremely large, and It can be seen that the operability during mixing is excellent and the viscosity increase is extremely excellent.

Further, from Example 2, even in a system having a high salt concentration, the thickening property of the present invention does not decrease so much, in particular, the compound (A) is a quaternary ammonium salt type cationic surfactant, It can be seen that when (B) is an anionic aromatic compound or a bromide compound, the viscosity increase hardly changes, which is better than Comparative Example 2 relating to the conventional thickener.

From Example 3, when the rheology modifier according to the present invention was used in a slurry system, the kneading time, slurry viscosity, separation resistance in water and It can be seen that the breathing amount is excellent.

Furthermore, from Examples 4 to 13, even when the rheology modifier according to the present invention is used in a cement slurry system having a high salt concentration, an inorganic oxide system, soil, etc., the kneading time is very fast, It can be seen that both the separation resistance in water and the amount of breathing water are excellent. On the other hand, in Comparative Examples 4, 5, 10, and 13 related to the conventional thickener, although the kneading time can be shortened slightly by adjusting the addition amount, the separation resistance in water and the amount of breathing water related to viscosity are increased. Is not getting satisfactory results. On the contrary, in order to improve the resistance to separation in water and the amount of breathing water, the amount of addition must be increased, and a slurry having good properties cannot be obtained in a short time. Further, from Examples 4, 5 and 13, in the system in which ordinary cement was used as the hydraulic powder, when the compound (B) was a sulfonate having an aromatic ring, kneading time, resistance to separation in water, It can be seen that the breathing water amount is excellent and the hydration rate is also excellent. In Comparative Examples 4, 5, and 6 related to the conventional thickener, the addition amount is adjusted,
When trying to improve the separation resistance in water and the amount of breathing, the hydration rate is delayed, and a slurry having good properties has not been obtained.

Example 14 For the slurry formulation II in Table 4, the compound (A),
The effect of using a dispersant in combination with (B) was measured. That is, at 20 ° C., the fine powder, water, the dispersant in Table 16 and the compound (B) were previously kneaded for 30 seconds, and then the compound (A) was added and kneaded with a mortar mixer until the fluidity remained unchanged. Here, the amount of the dispersant added was 1.
It was set to 0% by weight. After the slurry was prepared, the kneading time, the slurry flow value, the slurry viscosity, the separation resistance in water, the amount of breathing water, and the hydration rate were measured in the same manner as above.
The results are shown in Table 17.

[0145]

[Table 16]

[0146]

[Table 17]

The addition amount in Table 17 is the total effective concentration (% by weight) of the compound (A) and the compound (B) in the aqueous phase of the slurry.

Example 15 Under the mixing conditions shown in Table 18, a pan-type forced kneading mixer (55
L) Gravity method is used to add cement (C), fine aggregate (S) and coarse aggregate (G) and knead for 10 seconds to prepare a mixture containing the dispersant and compound (B) shown in Table 16. After adding water (W) and stirring for 2 minutes, compound (A) was added and 40 L of concrete was kneaded for 1 minute. The produced concrete was discharged onto a kneading plate, and the slump, the vibration isolation resistance test, the curing time and the 3 day strength were measured according to the test methods described below. The amount of the dispersant added was adjusted so that the slump value by the following method would be 18 cm.

1. Slump: Slump value (cm) according to JIS A 1101. Vibration isolation resistance test: diameter 15 cm x height 30 cm
The concrete manufactured under the mixing conditions shown in Table 1 is put into the columnar form of, and then it is installed and fixed on the table vibrator. Vibration condition 60Hz (1.5G horizontal, 0.22G vertical)
Then, after vibrating for 30 seconds, the thickness of the separated paste layer (the layer in which the aggregate has settled and does not exist) was measured on the upper surface of the mold. The evaluation criteria are as follows. ⊚: 1 cm or less O: more than 1 cm and 2 cm or less Δ: more than 2 cm and 3 cm or less x: more than 3 cm 3. Curing time: The setting time was measured by the proctor penetration resistance test of JIS A 6204. The evaluation criteria (starting time) are as follows. ○: 7 hours or less △: more than 7 hours and 9 hours or less ×: more than 9 hours 4. Strength test: Three-day strength was measured by the JIS A 1108 compressive strength test. The evaluation criteria are as follows. ○: Over 20 N / mm ² △: Over 15 N / mm ² 20 N / mm ² or less ×: 15 N / mm ² or less

[0150]

[Table 18]

The materials used in Table 18 are as follows. Water (W): Tap water cement (C): Normal Portland cement, commercial product,
Density 3.16 g / cm ³ Fine aggregate (S): River sand (external dry density 2.55 g / cm ³ , water absorption 1.94%, coarse grain ratio 2.73) Coarse aggregate (G): crushed stone Dry density 2.63 g / cm ³ , water absorption 0.93%, coarse grain ratio 6.71, maximum dimension 20 mm

[0152]

[Table 19]

The weight% in Table 19 is the effective component concentration based on the weight of the cement.

Example 16 Regarding an aqueous solution (sample aqueous solution) containing the compound (A) and the compound (B) in the combinations shown in Table 20,
The presence or absence of formation of reticulated aggregates was observed. Quick freeze the sample aqueous solution by crimping it on a copper plate cooled with liquid nitrogen.
It was performed using a field emission scanning electron microscope (abbreviation: FE-SEM) S-4000 (manufactured by Hitachi) equipped with a cryo unit. The scanning condition was 7.5 kV. The length and diameter between the intersections of the reticulated aggregate were measured and evaluated according to the following criteria. The results are shown in Table 20.

For example, the sample aqueous solution of Example 16-1 contained 1.6 parts by weight of hexadecyltrimethylammonium chloride [compound (A)] and 0.97 parts by weight of sodium p-toluenesulfonate [compound (B)]. Water 9
It was prepared by uniformly mixing 7.43 parts by weight. One drop of this aqueous solution was pressure-bonded on a copper plate, rapidly frozen, and observed. Similar observations were made for other examples. In addition, an image photograph showing a state in which a network-like aggregate is formed in the aqueous solution in Example 16-7 is shown in FIG. In FIG. 1, white mesh-like aggregates spread over the entire image can be confirmed.

(Length) ◯: 0.01 to 100 μm X: less than 0.01 μm or more than 100 μm (diameter) A: 0.05 μm or more and less than 2.0 μm ◯: 0.01 μm or more and less than 0.05 μm X: less than 0.01 μm

[0157]

[Table 20]

Example 17 Compound (A) and compound (B) in the combination shown in Table 21
SS was measured by the following method using a slurry prepared from, and water and powder (normal Portland cement).
At the same time, the turbidity was measured. The slurry was prepared by kneading water, powder and compound (B) with a hand mixer (MK-H3, manufactured by Matsushita Electric Industrial Co., Ltd.) for 30 seconds, then adding compound (A) and further stirring for 60 seconds. It was prepared, and its composition was 1 part by weight in total of the compound (A) and the compound (B) (the ratio of both is as shown in Table 21), 100 parts by weight of powder (ordinary Portland cement) and water. 100
Parts by weight.

Within 1 minute from the above slurry preparation, 500 m
500mL beaker containing L 20 ° C ion-exchanged water (JIS R 3503 compliant, borosilicate glass, diameter 85
mm, height 120 mm), 30 mL of slurry at 20 ° C.
Was charged for 15 seconds ± 5 seconds from a height of 3 cm from the water surface.
A mechanical mixer (HEIDON manufactured by Shinto Kagaku Co., Ltd.) that fixed the distance from the lower end surface of the stirring blade to the inner bottom surface of the beaker to 1.5 cm after standing for 10 seconds after adding the slurry.
BL600, blade type: anchor type, width x height = 68m
m.times.68 mm) and 60 r.p.m. p. m. And stirred for 10 seconds. After standing for 10 seconds, 5 mL of water was sampled at a position of a depth of 4.5 cm from the water surface and used as a sample for SS and turbidity measurement.

1. SS (Suspended Solid: Suspended Solids) Concentration Measurement Method 5 mL of the above sample is put in a sample dish of aluminum foil, and 105
After the water is volatilized at 2 ° C. for 2 hours, the mass of SS remaining in the sample dish is measured and the concentration is calculated. The evaluation criteria are shown below. ◎: 350 mg / L or less ○: 350 mg / L or more 500 mg / L or less ○ to Δ: 500 mg / L or more 1000 mg / L or less Δ: 1000 mg / L or more 1500 mg / L or less ×: 1500 mg / L or more

2. Turbidity Colorimetric color difference meter (Model ND-1001DP, manufactured by Nippon Denshoku Industries Co., Ltd., absorption cell length 10 mm, 12V5)
The turbidity was measured with a 0 W halogen lamp) within 1 minute after sampling, and evaluated according to the following criteria. Turbidity (%) = diffusivity (%) x 100 / total transmitted light rate (%) ◯: 6.0% or less △: more than 6.0% 30% or less x: more than 30%

[0162]

[Table 21]

Example 18 The storage elastic modulus G ′ was measured using an aqueous solution (a total of 5% by weight of the compound (A) and the compound (B) was added to water by a combination of the compounds shown in Table 22. Storage modulus G'is A
RES viscoelasticity measuring device (made by Rheometric Scientific), cone plate (diameter: 50 mm, angle: 0.0398 rad, GAP: 0.0508 mm)
, Strain 1.0%, measurement range 0.0628-6
It was measured under the conditions of 2.8 rad / s and 20 ° C. The G result from the angular velocity ω is in 1~10rad / s' _min /
_G'max was obtained and evaluated as follows. Further, to evaluate the G _{'ma x} at that time based on the following criteria. The measurement result of Example 18-7 is shown in FIG. As shown in FIG. 3, in this example, G ′ with an angular velocity ω of approximately 1 to 10 rad / s and substantially constant.
Taken up, G _'min is 39Pa (ω = 1rad / s) ,
G _'max is 48Pa (ω = 7.3rad / s) , G' min
/ _G'max was 0.8.

(Evaluation of _G'min / G ' _max ) ⊚: _G'min / G' _max is 0.7 or more and less than 1.0 ◯: _G'min / G ' _max is 0.5 or more and less than 0.7 _{△: G 'min / G'} max is 0.4 or more less than 0.5 _{×: G 'min / G'} max is less than 0.4 (G _'max rating) ◎: G' _max is 10-100 Pa ○: G _'max is 5～500Pa (where ◎ except those in the range of) △: G' _max is 2～1000Pa (excluding the range of ◎ and ○) ×: less than G _'max is 2Pa or 1000Pa Super

[0165]

[Table 22]

[0166]

The slurry rheology modifier of the present invention is
When imparting viscosity to the slurry, kneading for a short time exhibits sufficient viscosity, and even if prepared in advance as an aqueous solution, the viscosity of the aqueous solution is low and workability is excellent. Further, a slurry containing this slurry rheology modifier has high resistance in water and is unlikely to cause material separation.

[Brief description of drawings]

FIG. 1 is an image photograph showing a state in which a reticulated aggregate is formed in an aqueous solution in Example 16-7.

FIG. 2 is a schematic view showing a beaker used for measuring an SS (suspended particle) concentration and a stirring blade housed in the beaker according to a third aspect of the present invention.

FIG. 3 is an angular velocity ω in viscoelasticity measurement of Example 18-7.
It is a graph which shows the relationship between and storage elastic modulus G '.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C04B 24/20 C04B 24/20 C04B 103: 30 103: 30 103: 40 103: 40 (72) Inventor Shiba Daisuke 1334 Minato Minato, Wakayama City, Wakayama Prefecture F-term in Kao Research Laboratory (reference) 4G012 MB08

Claims (9)

[Claims] 1. A first water-soluble low-molecular compound [hereinafter referred to as a compound
And a second water different from the compound (A)
A soluble low molecular weight compound [hereinafter referred to as compound (B)]
A slurry rheology modifier having a compound
Aqueous solution S of (A) _A(Viscosity at 20 ° C is 100 mPa
s or less) and an aqueous solution S of the compound (B)_B(At 20 ° C
With a viscosity of 100 mPa · s or less) and 50/50
The viscosity of the aqueous solution mixed at a weight ratio of
At least 2 times higher than the viscosity of any aqueous solution before
A slurry rheology modifier that can be. 2. An aqueous solution obtained by mixing the aqueous solution S _A and the aqueous solution S _B at a weight ratio of 50/50 contains at least one compound different from the compound (A) and the compound (B), and at 20 ° C. The slurry rheology modifier according to claim 1, which has an electric conductivity of 0.1 to 80 mS / cm. 3. A slurry rheology modifier containing the compound (A) and the compound (B) according to claim 1, which is obtained by mixing the aqueous solution S _A and the aqueous solution S _{B according} to claim 1. A slurry rheology modifier capable of forming a reticulated association of the compound (A) and the compound (B) in an aqueous solution. 4. A slurry rheology modifier containing the compound (A) and the compound (B) according to claim 1, wherein the effective component of the compound (A) and the effective component of the compound (B) are combined. 1 part by weight (in this total, the weight ratio of the active ingredient of the compound (A) and the active ingredient of the compound (B) is (A) / (B) = 5 /
It is 95-95 / 5. ) And ordinary Portland cement (100 parts by weight) and water (100 parts by weight) at a temperature of 20 ° C. (30 mL) are added to 500 mL of a water (20 ° C.) in a 500 mL beaker at a position 3 cm from the water surface for 15 seconds ± 5 seconds. After standing for 2 seconds, a mechanical mixer (stirring blade type: anchor type, width x
Height = 68 mm × 68 mm), 60 r.p.m. p. m. In 1
3. Stir for 0 seconds, leave still for 10 seconds, and then set to a depth of 4.
A slurry rheology modifier having an SS (suspended particle) concentration of 1000 mg / L or less in water collected at a position of 5 cm. 5. A slurry rheology modifier containing the compound (A) and the compound (B) according to claim 1, wherein a total of 5 effective components of the compound (A) and the compound (B). Parts by weight (In this total, the weight ratio of the effective component of the compound (A) and the effective component of the compound (B) is (A) / (B) = 5/9.
It is 5 to 95/5. ) And 95 parts by weight of water at 20 ° C
A slurry rheology modifier whose aqueous solution satisfies the following characteristics. <Characteristics> Cone plate (diameter 50 mm, angle 0.03
98 rad, GAP0.0508mm) angular velocity ω is 1
~10rad / s minimum G _'min and a maximum value G' _max ratio G _'min / G' _max of storage modulus obtained in the range of 0.
It is 4-1. 6. A combination of the compound (A) and the compound (B) is a compound (A) selected from (1) an amphoteric surfactant.
And a combination of a compound (B) selected from an anionic surfactant, (2) a combination of a compound (A) selected from a cationic surfactant and a compound (B) selected from an anionic aromatic compound, 3) The slurry rheology modifier according to any one of claims 1 to 5, which is selected from a combination of a compound (A) selected from a cationic surfactant and a compound (B) selected from a brominated compound. 7. The slurry rheology modifier according to claim 1, wherein the effective ratio of the compound (A) and the compound (B) is a compound (A) / compound (B). = 1 /
A method for producing a slurry, which is added to the slurry so as to be 20 to 20/1. 8. The slurry rheology modifier according to any one of claims 1 to 6, wherein the sum of the effective components of the compound (A) and the compound (B) is the effective component concentration in the aqueous phase of the slurry. 0.
A method for producing a slurry, which is added to the slurry so as to have a content of 01 to 20% by weight. 9. A slurry containing one of the compound (A) or the compound (B) of the slurry rheology modifier according to any one of claims 1 to 6, a powder and water, and then preparing the slurry. A method for producing a slurry, wherein the other compound of the compound (A) or the compound (B) is added to the slurry.