JP6818732B2 - Rheology modifier - Google Patents

Description

The present invention relates to rheology modifiers and slurry compositions.

In many industrial products used in the form of an aqueous solution or a slurry, various kinds of additives are used for the purpose of improving their physical characteristics. For example, in order to modify the rheology of an aqueous solution or slurry, it may be desired to appropriately adjust the viscosity according to the purpose or application. Conventionally, in order to adjust the viscosity of an aqueous solution or a slurry, measures such as addition of a thickener or a thickener, heating or cooling operations, and adjustment of an electrolyte concentration have been taken. Further, it is known that the surfactant affects the viscosity, elasticity, thickening, etc. of the aqueous solution or slurry (Patent Documents 1 and 2).

In a hydraulic slurry containing a hydraulic powder such as cement, a rheology modifier may be used to improve physical properties such as viscosity and material separation resistance. According to Patent Document 3, by adding a specific anionic surfactant and a specific cationic surfactant to a cement slurry at a constant ratio, a pseudo polymer called a string-like micelle is formed to provide high viscoelasticity. It is disclosed that it is obtained. Since this pseudo polymer is constructed by intermolecular interactions other than covalent bonds such as hydrophobic bonds at the alkyl chain portion and peculiar interactions at the hydrophilic portion, the pseudo polymer is subjected to a certain shear force. It has the characteristic that the structure collapses and the viscoelasticity decreases (high thixotropy). Therefore, the pseudo-polymer structure collapses during transportation when shearing force is applied to reduce the viscosity, and the pseudo-polymer structure is regenerated and viscoelasticity is restored at the casting site where the shearing force is removed. It exhibits performance (both pumping property and viscoelasticity) that system thickeners do not have.

In the string-like micelle formed by the anionic surfactant and the cationic surfactant of Patent Document 3, the hydrophilic group is arranged outward (aqueous phase side) and the hydrophobic portion is arranged inward (oil phase side) in water. It is believed that there is. The viscoelasticity exhibited by string-shaped micelles correlates with the number of carbon atoms in the hydrophobic portion, and at temperatures above the Krafft point of the surfactant, the higher the number of carbon atoms, the higher the viscoelasticity at a constant temperature and addition amount. Viscoelasticity is expressed by the entanglement of string-shaped micelles, which are pseudopolymers, but when the string-shaped micelles are entangled with each other, there is a certain probability that the micelles will slip through each other. At this time, as the number of carbon atoms in the hydrophobic portion increases, the volume of the hydrophobic portion increases, and it becomes difficult for the string-shaped micelles to slip through each other. As a result, it is presumed that the probability of slipping through is reduced, the entanglement is strengthened, and the viscoelasticity of the entire system is improved.

Japanese Patent Publication No. 2014-502602 Japanese Unexamined Patent Publication No. 8-133805 Japanese Unexamined Patent Publication No. 2003-313536

According to the present invention, when added to an aqueous solution or slurry, viscoelasticity can be imparted to the aqueous solution or slurry in a wide temperature range (for example, 7 ° C to 32 ° C), particularly in a high temperature range of 32 ° C. Provided is a rheology modifier capable.

In the present invention, the (A) hydrocarbon group has 12 or more and 22 or less carbon atoms, and the average number of moles of alkylene oxide added is 0 or more and 25 or less, a sulfate ester or a salt thereof (hereinafter referred to as component (A)). , (B) Fatty acid alkanolamide having 10 or more and 22 or less carbon atoms in the fatty acid moiety (hereinafter referred to as (B) component), and (C) Carboxylic acid having 8 or more carbon atoms or a salt thereof (hereinafter, (C)). It relates to a rheology modifier containing (referred to as an ingredient).

The present invention also relates to a slurry composition containing the rheology modifier, water, and powder of the present invention.

According to the present invention, when added to an aqueous solution or slurry, viscoelasticity is imparted to the aqueous solution or slurry in a wide temperature range (for example, 7 ° C. to 32 ° C.), particularly in a high temperature range of 32 ° C. or the like. A rheology modifier that can be provided is provided.
Since the rheology modifier of the present invention can impart viscoelasticity to water in a wide temperature range from low temperature to high temperature (for example, 7 ° C to 32 ° C), particularly in a high temperature range of 32 ° C, for example, an aqueous solution or water. It is effective in modifying the rheology of the slurry containing. Since the slurry composition of the present invention has a high viscosity and is excellent in water separation resistance, it is effective in applications requiring pumping property and material separation resistance.

As a result of various studies, the present inventors have conducted a string in which a combination of a specific sulfate ester of component (A) or a salt thereof and a specific fatty acid alkanolamide of component (B) exhibits high viscoelasticity at a low concentration. It was found to form an ester. One of the factors that influence the micellar structure of a surfactant in water is the filling parameter of the surfactant. The filling parameters of the components (A) and (B) of the present invention are different from each other, and in a system in which these are mixed, a mixture of the components (A) and (B) is tentatively considered as a mixture thereof. It is presumed that the average (average in number of molecules) filling parameter is a value suitable for forming string-shaped micelles.
Then, in the present invention, by using a specific compound which is the component (C), an aqueous solution or a slurry is used in a wide temperature range from low temperature to high temperature (for example, 7 ° C. to 32 ° C.), particularly in a high temperature range of 32 ° C. It is possible to impart viscoelasticity to such substances. By adding the component (C), the component (C) is arranged between the string-shaped micelles composed of the component (A) and the component (B), and the internal density is improved, which becomes an optimum filling parameter. It is presumed that this is the reason.

<Rheology modifier>
The rheology modifier of the present invention contains a component (A), a component (B) and a component (C).
The rheology modifier of the present invention is preferably a liquid material, more preferably a liquid material containing water. An example of the rheology modifier of the present invention is a rheology modifier containing component (A), component (B), component (C) and water. As another example of the rheology modifier of the present invention, a string-shaped micelle containing (A) component, (B) component, (C) component and water and formed from (A) component and (B) component. Examples include rheology modifiers contained. When string-shaped micelles are formed, the rheology modifier of the present invention behaves in a dynamic viscoelasticity similar to the Maxwell type.

[(A) component]
The rheology modifier of the present invention contains, as the component (A), a sulfate ester or a salt thereof, which has a hydrocarbon group having 12 or more and 22 or less carbon atoms and an average addition molar number of alkylene oxide of 0 or more and 25 or less. contains.

The hydrocarbon group is preferably a linear or branched alkyl group or a linear or branched alkenyl group, more preferably a linear alkenyl group or a straight chain alkyl group, and even more preferably a straight chain. It is an alkenyl group.
The number of carbon atoms of the hydrocarbon group is 12 or more, preferably 14 or more, more preferably 16 or more, still more preferably 18 or more, and 22 or less, preferably 20 or less, from the viewpoint of obtaining high viscoelasticity.

The hydrocarbon group includes, for example, one or more selected from a lauryl group, a myristyl group, a palmityl group, an oleyl group, a stearyl group and a docosyl group, and is preferably selected from a myristyl group, a palmityl group, an oleyl group and a stearyl group. It is one or more, more preferably one or more selected from a palmityl group, an oleyl group and a stearyl group, still more preferably an oleyl group or a stearyl group, and even more preferably an oleyl group.

The average number of moles of alkylene oxide added is 0 or more and 25 or less.
Examples of the alkylene oxide include alkylene oxides having 2 or more and 4 or less carbon atoms. The alkylene oxide is preferably ethylene oxide. The component (A) preferably contains ethylene oxide as an alkylene oxide.

When the hydrocarbon group of the component (A) has 12 or more and 16 or less carbon atoms, the average number of moles of alkylene oxide added is preferably 1 or more, more preferably 2 or more, and from the viewpoint of solubility in water. From the viewpoint of increasing the arrangement density of the activator in the string-shaped micelle, it is preferably 20 or less, more preferably 16 or less, still more preferably 14 or less, still more preferably 12 or less, still more preferably 10 or less, still more preferably. It is 8 or less, more preferably 6 or less.
When the number of carbon atoms of the hydrocarbon group of the component (A) is 17 or more and 22 or less, the average number of moles of alkylene oxide added is preferably 2 or more, more preferably 4 or more, still more preferably, from the viewpoint of solubility in water. Is 5 or more, and from the viewpoint of increasing the arrangement density of the active agent in the string-shaped micelle, it is preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less, still more preferably 12. It is as follows.

Examples of the sulfate ester salt of the component (A) include inorganic salts selected from sodium salt, ammonium salt, potassium salt, calcium salt, magnesium salt and the like, monoethanolammonium salt, diethanolammonium salt, triethanolammonium salt, morpholinium salt and the like. Organic ammonium salts selected from are suitable.

Specific examples of the component (A) include alkyl sulphate, alkenyl sulphate, polyoxyalkylene alkyl ether sulphate, polyoxyalkylene alkenyl ether sulphate, alkyl phenyl sulphate, alkenyl phenyl sulphate, polyoxyalkylene alkyl phenyl ether sulphate and polyoxy. Examples thereof include alkylene alkenyl phenyl ether sulfate, and from the viewpoint of obtaining high viscoelasticity, one or more selected from alkenyl sulphate, polyoxyalkylene alkyl ether sulphate, and polyoxyalkylene alkenyl ether sulphate are preferable, and polyoxyalkylene alkyl ether sulphate, And one or more selected from polyoxyalkylene alkenyl ether sulfate are more preferable.

As the component (A), a compound represented by the following general formula (a1) is suitable from the viewpoint of obtaining high viscoelasticity.
R ^1a- O- (R ^2a O) _n- SO ₃ M ¹ (a1)
[In the formula, R ^1a is a hydrocarbon group having 12 or more and 22 or less carbon atoms, R ^2a is an alkylene group having 2 or more and 4 or less carbon atoms, preferably an ethylene group, and n is the average number of moles added. It is a number of 0 or more and 25 or less. M ¹ is a hydrogen atom or a cation, preferably an inorganic or organic cation. ]

In the general formula (a1), R ^1a is preferably a linear or branched alkyl group or a linear or branched alkenyl group, more preferably a linear alkenyl group or a linear alkyl group. More preferably, it is a straight chain alkenyl group.
The carbon number of R ^1a is 12 or more, preferably 14 or more, more preferably 16 or more, still more preferably 18 or more, and 22 or less, preferably 20 or less, from the viewpoint of obtaining high viscoelasticity.

In the general formula (a1), from the viewpoint of obtaining high viscoelasticity, R ^1a includes, for example, one or more selected from lauryl group, myristyl group, palmitic acid group, oleyl group, linoleic group, stearyl group and docosyl group. , Preferably one or more selected from myristyl group, palmitic acid group, linole group, oleyl group and stearyl group, and more preferably one or more selected from linole group, palmitic acid group, oleyl group and stearyl group. It is preferably one or more selected from a linoleic group, an oleyl group, and a stearyl group, more preferably an oleyl group or a stearyl group, and even more preferably an oleyl group. Further, R ^1a is more preferably an oleyl group when the temperature of the aqueous solution or slurry to which the rheology modifier is added is near room temperature, for example, about 15 ° C. to about 30 ° C. Further, R ^1a is more preferably a stearyl group when the temperature of the aqueous solution or slurry to which the rheology modifier is added is relatively high, for example, about 30 ° C. to about 50 ° C.

In the general formula (a1), when the number of carbon atoms of R ^1a is 12 or more and 16 or less, n is preferably 1 or more, more preferably 2 or more, and in a string-shaped micelle from the viewpoint of solubility in water. From the viewpoint of increasing the arrangement density of the surfactant, it is preferably 20 or less, more preferably 16 or less, still more preferably 14 or less, still more preferably 12 or less, still more preferably 10 or less, still more preferably 8 or less, and more. More preferably, it is 6 or less.
In the general formula (a1), when the carbon number of R ^1a is 17 or more and 22 or less, n is preferably 2 or more, more preferably 4 or more, still more preferably 5 or more, and from the viewpoint of solubility in water. From the viewpoint of increasing the arrangement density of the surfactant in the string-shaped micelle, it is preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less, still more preferably 12 or less.

In the general formula (a1), M ¹ is a hydrogen atom, or an inorganic cation such as sodium ion, ammonium ion, potassium ion, calcium ion, magnesium ion, monoethanolammonium ion, diethanolammonium ion, triethanolammonium ion, morpholi. Examples thereof include organic cations such as nium ion, preferably inorganic cations of sodium ion, potassium ion, ammonium ion, calcium ion and magnesium ion, and more preferably sodium ion or ammonium ion.

The average filling parameter of the component (A) is preferably 1/3 or more and 1 or less from the viewpoint of obtaining high viscoelasticity. In the present invention, the average filling parameters of the component (A), the component (B), etc. are represented by the following equations.
Average filling parameter = v / (a0 × lc)
v: Volume of hydrocarbon group a0: Optimal head area of water interface of surfactant lc: Critical chain length of hydrocarbon chain

[Component (B)]
The rheology modifier of the present invention contains, as the component (B), a fatty acid alkanolamide having a fatty acid portion having 10 or more and 22 or less carbon atoms.

The hydrocarbon group of the fatty acid moiety is a hydrocarbon group containing a carbon atom of a carboxyl group in the raw material fatty acid of the fatty acid alkanolamide, preferably a linear alkyl group and / or a linear alkenyl group.

The carbon number of the fatty acid portion is the number of carbon atoms including the carbon atom of the carboxyl group in the raw material fatty acid of the fatty acid alkanolamide, and is 10 or more, preferably 12 or more, more preferably 14 or more, still more preferable, from the viewpoint of obtaining high viscoelasticity. Is 16 or more, and 22 or less, preferably 20 or less, still more preferably 18 or less, and even more preferably 18.

Examples of the fatty acid alkanolamide include fatty acid monoethanolamide, fatty acid methylmonoethanolamide, fatty acid ethylmonoethanolamide, fatty acid propylmonoethanolamide, fatty acid methanolethanolamide, fatty acid diethanolamide, and the like, from the viewpoint of obtaining high viscous elasticity. Fatty acid diethanolamide is preferred.

Examples of the component (B) include oleic acid diethanolamide, stearic acid diethanolamide, palm nuclear fatty acid diethanolamide, coconut fatty acid diethanolamide, myristic acid diethanolamide, lauric acid diethanolamide, and the like, and two or more of these are used in combination. You may. The component (B) is preferably selected from oleic acid diethanolamide, palm nuclear fatty acid diethanolamide, coconut fatty acid diethanolamide, and lauric acid diethanolamide from the viewpoint of maintaining solubility in water and obtaining high viscoelasticity. One or more, more preferably one or more selected from oleic acid diethanolamide and lauric acid diethanolamide.

From the viewpoint of increasing the viscoelasticity of the slurry at low temperature, the rheology modifier of the present invention contains the fatty acid alkanolamide (hereinafter, (B1) component) having a fatty acid portion having 15 or more and 22 or less carbon atoms as the component (B). ), And a fatty acid alkanolamide (hereinafter referred to as (B2) component) having a fatty acid portion having 10 or more and 14 or less carbon atoms is preferably contained.
The component (B1) is preferably a fatty acid alkanolamide having 16 or more and 18 or less carbon atoms in the fatty acid portion, and more preferably oleic acid diethanolamide and / or stearic acid diethanolamide.
The component (B2) is preferably a fatty acid alkanolamide having a fatty acid portion having 10 or more and 12 or less carbon atoms, and more preferably a capric acid diethanolamide and / or a lauric acid diethanolamide.

The component (B) is obtained by reacting a higher fatty acid with an alkanolamine, and by-products other than the fatty acid alkanolamide are simultaneously produced. Examples of by-products include fatty acid alkanolamide fatty acid monoesters in which fatty acids are dehydrated and condensed, fatty acid alkanolamide fatty acid diesters, fatty acid alkanolamine monoesters in which alkanolamines and fatty acids are dehydrated and condensed, and fatty acid alkanolamine diesters. The component (B) of the present invention may contain a small amount of the above-mentioned by-product as long as the effect of the present invention is not impaired. The content of the by-product in the component (B) is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and further preferably 5 parts by mass in 100 parts by mass of the component (B) from the viewpoint of obtaining high viscoelasticity. It is less than a part.

The average filling parameter of the component (B) is preferably 1/2 or more and 2 or less from the viewpoint of obtaining high viscoelasticity.

[Component (C)]
The rheology modifier of the present invention contains a carboxylic acid having 8 or more carbon atoms or a salt thereof as the component (C). The component (C) is preferably a monovalent carboxylic acid having 8 or more carbon atoms or a salt thereof, and more preferably a fatty acid having 8 or more carbon atoms or a salt thereof, from the viewpoint of exhibiting viscoelasticity of the slurry in a wide temperature range.

The carbon number of the component (C) is 8 or more, preferably 10 or more, more preferably 12 or more, still more preferably 14 or more, still more preferably 16 or more, from the viewpoint of developing the viscoelasticity of the slurry in a wide temperature range. Then, it is preferably 22 or less, more preferably 20 or less, and further preferably 18 or less.
(C) the number of carbon atoms of the component (A) is the number of carbon atoms of the hydrocarbon groups of component viscoelasticity of the slurry in a wide temperature range that (formula (a1) R number of carbon atoms of ^1a in) to be close range It is preferable from the viewpoint of expression.
The carbon number of the component (C) is X (integer) when the carbon number of the hydrocarbon group of the component (A) (the carbon number of R ^{1a in} the general formula (a1)) is X (integer) from the viewpoint of the filling parameter. It is preferably in the range of ± 2, and more preferably X (that is, the carbon number of the (C) component and the hydrocarbon group of the (A) component are the same).

Examples of the component (C) include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, arachidic acid, behenic acid, lignoceric acid, and linoleic acid, and two or more of them. It may be used together. The component (C) is preferably one or more selected from capric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid from the viewpoint of developing viscoelasticity in a wide temperature range, and capric acid, One or more selected from lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid are more preferable, and one or more selected from palmitic acid, stearic acid, and oleic acid are further preferable, stearic acid, and oleic acid. One or more selected from the above is even more preferable.
The component (C) is preferably a saturated fatty acid when the hydrocarbon group of the component (A) (R ^1a in the general formula (a1)) is an alkyl group, and the hydrocarbon group of the component (A) (general). When R ^1a ) in the formula (a1) is an alkenyl group, it is preferably an unsaturated fatty acid. For example, when the hydrocarbon group of the component (A) (R ^1a in the general formula (a1)) is a stearyl group, the component (C) is preferably stearic acid, and the hydrocarbon group of the component (A) (general). When R ^1a ) in the formula (a1) is an oleyl group, the component (C) is preferably oleic acid.

[Composition of rheology modifier, etc.]
The rheology modifier of the present invention contains the component (A) in an amount of preferably 0.25% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, from the viewpoint of obtaining high viscoelasticity. More preferably 5% by mass or more, even more preferably 10% by mass or more, and from the viewpoint of ensuring the fluidity of the composition, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15. Contains less than% by mass.

The rheology modifier of the present invention contains the component (B) in an amount of preferably 0.25% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% or more by mass, from the viewpoint of obtaining high viscoelasticity. More preferably 5% by mass or more, even more preferably 10% by mass or more, and from the viewpoint of ensuring the fluidity of the composition, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15. Contains less than% by mass.

In the rheology modifier of the present invention, when the component (B1) and the component (B2) are contained as the component (B), the mass ratio (B1) of the content of the component (B1) to the content of the component (B2) ) / (B2) is preferably 0.5 or more, more preferably 2.0 or more, still more preferably 4.0 or more, and preferably 10.0 or less, from the viewpoint of increasing the viscoelasticity of the slurry at low temperature. , More preferably 7.0 or less, still more preferably 6.0 or less.

When the rheology modifier of the present invention contains water, the total content of the components (A) and (B) is preferably 0.5% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of obtaining high viscoelasticity. 1% by mass or more, more preferably 2% by mass or more, still more preferably 10% by mass or more, still more preferably 20% by mass or more, and preferably 99% by mass or less, more preferably 50% by mass or less, still more preferable. Is 40% by mass or less, more preferably 30% by mass or less.
In the rheology modifier of the present invention, the total content of the component (A) and the component (B) is within a predetermined range, and the respective contents of the component (A) and the component (B) are within a predetermined range. It is preferable to have.

In the rheology modifier of the present invention, the mass ratio (A) / (B) of the component (A) to the component (B) is preferably 3/97 or more, more preferably 10 /, from the viewpoint of obtaining high viscoelasticity. 90 or more, more preferably 20/80 or more, even more preferably 30/70 or more, even more preferably 40/60 or more, and preferably 95/5 or less, more preferably 90/10 or less, still more preferably 80. It is /20 or less, more preferably 70/30 or less, and even more preferably 60/40 or less.

The rheology modifier of the present invention preferably contains the component (C) in an amount of 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.2% by mass or more, from the viewpoint of developing the viscoelasticity of the slurry in a wide temperature range. Is 0.25% by mass or more, and is preferably 4.0% by mass or less, more preferably 3.0% by mass or less, still more preferably 2.0% by mass, from the viewpoint of maintaining the viscoelasticity of the slurry in a wide temperature range. % Or less.

In the rheology modifier of the present invention, the mass ratio ((A) + (B)) / (C) of the total content of the component (A) and the component (B) to the content of the component (C) is From the viewpoint of developing the viscoelasticity of the slurry in a wide temperature range, it is preferably 6.0 or more, more preferably 8.0 or more, still more preferably 10.0 or more, still more preferably 12.0 or more, and preferably. Is 200 or less, more preferably 150 or less, still more preferably 125 or less, still more preferably 100 or less, still more preferably 75 or less, still more preferably 50 or less, still more preferably 25 or less.

The rheology modifier of the present invention is preferably a liquid material from the viewpoint of workability (easy to measure, immediately soluble in water, etc.).
Further, the rheology modifier of the present invention is preferably a liquid substance containing water from the viewpoint of making it a non-dangerous substance (or a flash point is not detected).
The rheology modifier of the present invention contains water, preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 22% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass. Hereinafter, it is more preferably contained in an amount of 35% by mass or less. Water is preferably used in an amount that is the balance of the rheology modifier of the present invention.

The rheology modifier of the present invention is a viewpoint of forming the rheology modifier of the present invention into a one-component type having a viscosity that is easy to handle when the rheology modifier of the present invention contains a liquid substance, that is, water. Therefore, as the component (D), it is preferable to contain a compound having a hydroxy group having an octanol / water partition coefficient of −1.6 or more and 1.2 or less. However, the component (C) is excluded from the component (D).

In the present invention, the octanol / water partition coefficient of the component (D) is a coefficient indicating the affinity of the organic compound for water and 1-octanol, which is represented by a logP value. The 1-octanol / water partition coefficient P is the partition equilibrium when a trace amount of compound is dissolved as a solute in a solvent of a two-component phase of 1-octanol and water, and is the ratio of the equilibrium concentrations of the compounds in each solvent. It is generally shown in the form of their log P for the base 10. LogP values for many compounds have been reported, and many values are listed in databases available from Daylight Chemical Information Systems, Inc. (Daylight CIS) and others for reference. If there is no actually measured logP value, it can be calculated by the program "CLOGP" etc. available from Daylight CIS. This program outputs the value of "calculation logP (ClogP)" calculated by Hansch, Leo's fragment approach together with the actually measured logP value, if any.

The fragment approach is based on the chemical structure of the compound and takes into account the number of atoms and the type of chemical bond (cf. A. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, PG Sammens, JBTaylor and CA Ramsden, Eds., P.295, Pergamon Press, 1990). This ClogP value can be used in place of the measured logP value when selecting a compound. In the present invention, if there is an actually measured value of logP, it is used, and if not, the ClogP value calculated by the program CLOGP v4.01 is used. Hereinafter, the octanol / water partition coefficient may be referred to as Log Pow.

The component (D) is preferably a compound having 1 or more and 10 or less carbon atoms.
The component (D) is preferably a compound having 1 or more and 3 or less hydroxy groups. The component (D) is preferably one or more compounds selected from a compound having one hydroxy group and a compound having two hydroxy groups.
The component (D) is preferably a compound having a molecular weight of 50 or more and 200 or less.

The component (D) is preferably an organic compound having a hydroxy group, more preferably an aliphatic compound having a hydroxy group, further preferably having one or two hydroxy groups, and having a carbon-carbon bond. It is an aliphatic compound having a saturated bond, and more preferably, it is an aliphatic compound having two hydroxy groups and having a carbon-carbon bond having a saturated bond and having 5 or less carbon atoms.

The component (D) is preferably a compound having a solubility parameter (Fedors method) of 9 or more, further 10 or more, and 20 or less, further 18 or less, from the viewpoint of obtaining high viscoelasticity. Hereinafter, the solubility parameter (Fedors method) may be referred to as an SP value.

The component (D) is preferably an organic compound having a hydroxy group. Examples of the organic compound having a hydroxy group include one or more compounds selected from the following (D1) and (D2).
(D1) Aromatic compound having a hydroxy group Specific examples thereof include benzyl alcohol (Log Pow 1.10 / SP value 9.3).
(D2) An aliphatic compound having a hydroxy group Specifically, diethylene glycol monobutyl ether (Log Pow 0.56 / SP value 10.5), 2-butoxyethanol (Log Pow 0.83 / SP value 10.8), ethylene glycol monoisopropyl ether (Log Pow). 0.05 / SP value 11.1), 1-butanol (LogPow 0.90 / SP value 11.3), 2-methoxyethanol (Log Pow -0.77 / SP value 12.0), triethylene glycol monobutyl ether (Log Pow 0.02 / SP value 10.3), Ethylene glycol monobutyl ether (Log Pow 1.15 / SP value 10.4) propyl propylene glycol (Log Pow 0.62 / SP value 10.5), 2-dimethylaminoethanol (Log Pow -0.58 / SP value 11.3), diethanolamine (Log Pow -1.43 / SP value) 15.4), 2-methylpentane-2,4-diol (Log Pow 0.58 / SP value 13.1), dipropylene glycol (Log Pow -0.70 / SP value 13.3), 1,3-butanediol (Log Pow -0.85 / SP) Value 14.8), 1,4-butanediol (Log Pow -1.00 / SP value 15.0), diethylene glycol (LogPow -1.30 / SP value 15.0), neopentyl glycol (Log Pow 0.23 / SP value 13.8), propylene glycol (Log Pow) -0.92 / SP value 15.9), ethylene glycol (Log Pow -1.36 / SP value 17.8), etc.

The component (D) is preferably an aliphatic compound having a (D2) hydroxy group, and more preferably an aliphatic compound having one or two hydroxy groups and having a saturated carbon-carbon bond. More preferably, it is an aliphatic compound having two hydroxy groups and having a saturated carbon-carbon bond and having 5 or less carbon atoms.

The component (D) is preferably diethanolamine (Log Pow -1.43 / SP value 15.4), 2-methylpentane-2,4-diol (Log Pow 0.58 / SP value 13.1), dipropylene glycol (Log Pow -0.70 /). SP value 13.3), 1,3-butanediol (Log Pow -0.85 / SP value 14.8), 1,4-butanediol (Log Pow -1.00 / SP value 15.0), diethylene glycol (Log Pow -1.30 / SP value 15.0), Neopentyl glycol (Log Pow 0.23 / SP value 13.8), propylene glycol (Log Pow -0.92 / SP value 15.9), and ethylene glycol (Log Pow)
It is one or more compounds selected from -1.36 / SP value 17.8).
The component (D) is more preferably 1,3-butanediol (Log Pow -0.85 / SP value 14.8), 1,4-butanediol (Log Pow -1.00 / SP value 15.0), and diethylene glycol (Log Pow -1.30). / SP value 15.0), neopentyl glycol (Log Pow 0.23 / SP value 13.8), propylene glycol (Log Pow -0.92 / SP value 15.9), and ethylene glycol (Log Pow -1.36 / SP value 17.8). These are the above compounds.
The component (D) is preferably one or more compounds selected from neopentyl glycol (Log Pow 0.23 / SP value 13.8) and propylene glycol (Log Pow -0.92 / SP value 15.9) from the viewpoint of odor and availability. ..

From the viewpoint of obtaining a liquid rheology modifier having a low viscosity with a small amount of the component (D) added, the octanol / water partition coefficient of the component (D) is preferably 0.03 or more, more preferably 0.7 or more, and , 1.15 or less, more preferably 0.85 or less. Compounds having an octanol / water partition coefficient in this range include benzyl alcohol, 1-butanol, 2-butoxyethanol, 2-methylpentane-2,4-diol, diethylene glycol monobutyl ether, neopentyl glycol, and ethylene glycol monoisopropyl ether. Preferably, 2-butoxyethanol is more preferred.

From the viewpoint of obtaining a liquid rheology modifier having a low viscosity with a small amount of the component (D) added, the SP value of the component (D) is preferably 9 or more, more preferably 10.7 or more, and 11.5 or less. Is preferable, 11.2 or less is more preferable, and 11 or less is further preferable. As those having an SP value in this range, benzyl alcohol, diethylene glycol monobutyl ether, 2-butoxyethanol, ethylene glycol monoisopropyl ether and 1-butanol are preferable, and benzyl alcohol, diethylene glycol monobutyl ether, 2-butoxyethanol and ethylene glycol monoisopropyl are preferable. Ether is more preferred, benzyl alcohol, diethylene glycol monobutyl ether and 2-butoxyethanol are even more preferred, and 2-butoxyethanol is even more preferred.

If the octanol / water partition coefficient is within the range of the component (D), the component (D) includes 2-dimethylaminoethanol (Log Pow -0.58 / SP value 11.3) having a hydroxy group and an amino group, and diethanolamine ( Compounds such as Log Pow -1.43 / SP value 15.4) can be used. From the viewpoint of obtaining a stable liquid rheology modifier having a viscosity that is easy to handle, the component (D) is preferably a compound having no amino group.

The rheology modifier of the present invention contains benzyl alcohol, diethylene glycol monobutyl ether, propylene glycol, 2-butoxyethanol, ethylene glycol monoisopropyl ether, 1-butanol, and 2-methylpentane-2,4-diol as the component (D). , And one or more compounds selected from neopentyl glycol are preferably contained.
From the viewpoint of imparting high viscoelasticity to the object with little influence on the component (A) and maintaining product stability at low temperature, the rheology modifier of the present invention has two or more kinds of components (D). Is preferably contained. From this point of view, the rheology modifier of the present invention contains benzyl alcohol, diethylene glycol monobutyl ether, 2-butoxyethanol, ethylene glycol monoisopropyl ether, 1-butanol, 2-methylpentane-2,4- as the component (D). It preferably contains two or more kinds selected from diol, propylene glycol and neopentyl glycol, and preferably contains propylene glycol and neopentyl glycol. When propylene glycol and neopentyl glycol are contained as the component (D), the mass ratio of propylene glycol / neopentyl glycol is preferably 20/80 or more, more preferably 30/70 or more, still more preferably 40/60 or more. And preferably 80/20 or less, more preferably 70/30 or less, still more preferably 60/40 or less.

Compounds whose Log Pow is outside the scope of the present invention even if they have a hydroxy group, such as glycerin (Log Pow -1.76 / SP value 16.5), and hydroxy groups even if Log Pow is within the range of the present invention. For compounds that do not have, for example, methylamine (Log Pow -0.71 / SP value 8.85), dimethylamine (Log Pow -0.20 / SP value 7.72), tetramethylethylenediamine (Log Pow 0.30 / SP value 7.74), It is considered that liquefaction is difficult and a stable rheology modifier having a viscosity that is easy to handle cannot be obtained.

When the component (D) is a compound having an octanol / water partition coefficient of 1 or more and 1.2 or less, the content of the component (D) is preferably 3% by mass or more in the rheology modifier of the present invention. , More preferably 4% by mass or more, preferably 30% by mass or less, more preferably 15% by mass or less, still more preferably 7% by mass or less.
When the component (D) is a compound having an octanol / water partition coefficient of 0.5 or more and less than 1, the content of the component (D) is determined by the rheology of the present invention from the viewpoint of the viscosity of the rheology modifier. Among the modifiers, preferably 3% by mass or more, more preferably 7.5% by mass or more, still more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably. Is 40% by mass or less.
When the component (D) is a compound having an octanol / water partition coefficient of 0 or more and less than 0.5, the content of the component (D) is determined by the rheology of the present invention from the viewpoint of the viscosity of the rheology modifier. Among the modifiers, preferably 3% by mass or more, more preferably 7.5% by mass or more, still more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably. Is 40% by mass or less, more preferably 25% by mass or less.
When the component (D) is a compound having an octanol / water partition coefficient of −0.8 or more and less than 0, the content of the component (D) is preferably 3 in the rheology modifier of the present invention. It is 0% by mass or more, more preferably 7% by mass or more, further preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less.
When the component (D) is a compound having an octanol / water partition coefficient of −0.95 or more and less than −0.8, the content of the component (D) is determined in the rheology modifier of the present invention. It is preferably 15% by mass or more, more preferably 22% by mass or more, still more preferably 30% by mass or more, still more preferably 35% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less. ..
When the component (D) is a compound having an octanol / water partition coefficient of −1.6 or more and less than −0.95, the content of the component (D) is determined in the rheology modifier of the present invention. It is preferably 25% by mass or more, more preferably 30% by mass or more, further preferably 35% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less.

When the rheology modifier of the present invention contains a plurality of compounds of the component (D), the content of at least one compound is preferably in the above range. For example, when the rheology modifier of the present invention contains two kinds of the compound of the component (D), it is preferable that the content of at least one compound is in the above range.

When the component (D) is a compound having an SP value of 9 or more and less than 10, the content of the component (D) is preferably 3% by mass or more, more preferably 4 in the rheology modifier of the present invention. It is by mass or more, preferably 30% by mass or less, more preferably 15% by mass or less, still more preferably 7% by mass or less.
When the component (D) is a compound having an SP value of 10 or more and less than 13, the content of the component (D) is preferably in the rheology modifier of the present invention from the viewpoint of the viscosity of the rheology modifier. Is 3% by mass or more, more preferably 7% by mass or more, further preferably 15% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less.
When the component (D) is a compound having an SP value of 13 or more and less than 13.5, the content of the component (D) is determined in the rheology modifier of the present invention from the viewpoint of the viscosity of the rheology modifier. , Preferably 3% by mass or more, more preferably 7% by mass or more, still more preferably 15% by mass or more, still more preferably 25% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, further. It is preferably 40% by mass or less.
When the component (D) is a compound having an SP value of 13.5 or more and less than 14.5, the content of the component (D) is the rheology modification of the present invention from the viewpoint of the viscosity of the rheology modifier. In the agent, preferably 3% by mass or more, more preferably 7% by mass or more, further preferably 15% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less. Even more preferably, it is 25% by mass or less.
When the component (D) is a compound having an SP value of 14.5 or more and less than 15.5, the content of the component (D) is the rheology modification of the present invention from the viewpoint of the viscosity of the rheology modifier. In the agent, preferably 3% by mass or more, more preferably 7% by mass or more, still more preferably 15% by mass or more, still more preferably 25% by mass or more, still more preferably 35% by mass or more, and preferably 70% by mass. % Or less, more preferably 60% by mass or less, still more preferably 45% by mass or less.
When the component (D) is a compound having an SP value of 15.5 or more and less than 18, the content of the component (D) is determined in the rheology modifier of the present invention from the viewpoint of the viscosity of the rheology modifier. , Preferably 3% by mass or more, more preferably 7% by mass or more, still more preferably 15% by mass or more, still more preferably 25% by mass or more, still more preferably 35% by mass or more, still more preferably 45% by mass or more. , And preferably 70% by mass or less, more preferably 60% by mass or less.
When the component (D) is a compound having an SP value of 18 or more and 20 or less, the content of the component (D) is preferably among the rheology modifiers of the present invention from the viewpoint of the viscosity of the rheology modifier. Is 25% by mass or more, more preferably 35% by mass or more, further preferably 45% by mass or more, and preferably 55% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less.

The rheology modifier of the present invention comprises (E) polyethylene glycol having a weight average molecular weight of 500 or more, polypropylene glycol having a weight average molecular weight of 500 or more, a copolymer of ethylene oxide and propylene oxide having a weight average molecular weight of 500 or more, and a hydrocarbon group. It is preferable to contain one or more compounds selected from ether compounds having a polyoxyalkylene group (however, the component (A) is excluded) [hereinafter referred to as the component (E)]. The component (E) is a preferable component from the viewpoint of exhibiting a good rheology-modifying effect even when the object to which the rheology modifier of the present invention is applied, for example, a hydraulic slurry contains bentonite.

The weight average molecular weight of the polyethylene glycol as the component (E) is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 5,000 or more, and preferably 5,000 or more, from the viewpoint of the viscosity of the rheology modifier. It is 20,000 or less, preferably 150,000 or less, more preferably 120,000 or less, still more preferably 90,000 or less, even more preferably 50,000 or less, still more preferably 20,000 or less.
The weight average molecular weight of polypropylene glycol as a component (E) is preferably 500 or more, more preferably 700 or more, and preferably 5,000 or less, more preferably 3,000 or less.
The weight average molecular weight of the copolymer of ethylene oxide and propylene oxide as the component (E) is preferably 1,000 or more, more preferably 2,000 or more, and preferably 25,000 or less, more preferably 20,000 or less. Is.

The weight average molecular weight of the component (E) is a value measured by a gel permeation chromatography (GPC) method using polystyrene as a standard, and when the component (E) is polyethylene glycol, water / ethanol can be used as a solvent. ..

Among the components (E), one or more compounds selected from the ether compounds having a hydrocarbon group and a polyoxyalkylene group have a hydrocarbon group having preferably 10 or more and 22 or less carbon atoms. The polyoxyalkylene group is preferably a group selected from a polyoxyethylene group and a polyoxypropylene group, and more preferably a polyoxyethylene group. The average number of moles of the polyoxyalkylene group added is preferably 9 or more and 5,000 or less.

From the viewpoint that a compound having a wide weight average molecular weight can be used, the component (E) is one or more selected from polyethylene glycol having a weight average molecular weight of 500 or more and a copolymer of ethylene oxide and propylene oxide having a weight average molecular weight of 500 or more. Polymers are preferred, and one or more polymers selected from polyethylene glycols having a weight average molecular weight of 500 or more are more preferred.

When the rheology modifier of the present invention contains the component (E), the component (E) is preferably 5% by mass or more, more preferably 6% by mass or more, still more preferably 7.5% by mass or more, and It is preferably contained in an amount of 20% by mass or less, more preferably 15% by mass or less, still more preferably 13% by mass or less.

From the viewpoint of workability, the viscosity of the rheology modifier of the present invention is preferably 1500 mPa · s or less, more preferably 1,000 mPa · s or less, still more preferably 800 mPa · s or less, still more preferably 800 mPa · s or less, at 20 ° C. It is 500 mPa · s or less. Here, as for the viscosity of the rheology modifier, 50 g of the liquid rheology modifier to be measured is put into a screw tube (Maruem, No. 7, 35 mm × 78 mm), and a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., It is a value measured after 3 minutes by stirring at a rotation speed of 12 rpm using a VISCOMETER TVB-10 (rotor M21).

When the rheology modifier of the present invention contains water, it contains a string-shaped micelle formed from the component (A) and the component (B). When this string-shaped micelle is added to the water to be pumped in the pipe, it has the effect of suppressing turbulence and frictional resistance between the water and the pipe, and suppressing the energy loss of pumping, but unlike conventional polymers, Even if the structure is destroyed by the strong shearing force of the pump, the string-shaped micelle structure is regenerated if it passes through the pump and the shearing force is reduced, so that it is suitable as a composition for reducing the pumping energy of water.
Due to these characteristics, the rheology modifier of the present invention is also suitably used as a thickener, thixotropy-imparting agent, and the like in applications requiring appropriate viscoelasticity. For example, it is useful as a thickening gelling agent, a pipe friction resistance reducing agent, an ink additive, a pesticide aid, a lubricant, a wax and the like.
The rheology modifier of the present invention is more useful as a rheology modifier for hydraulic slurries. That is, it is more useful as a rheology modifier for slurries containing hydraulic powder. The rheology modifier of the present invention can impart effects such as suppression of material separation and suppression of separation in water to a hydraulic slurry. The rheology modifier of the present invention can be used, for example, for underwater inseparable concrete, spray concrete, tunnel repair, construction on non-horizontal walls, additives for well excavation, and shield method. Further, the rheology modifier of the present invention can be used for revetment work without draining the water in the frame by surrounding the construction area with a frame.

In the rheology modifier of the present invention, it can be confirmed by electron micrographs that string-shaped micelles are formed from the components (A) and (B).

Further, in the rheology modifier of the present invention, when string-like micelles are formed from the components (A) and (B), the dynamic viscoelasticity of the composition exhibits behavior similar to that of the Maxwell type. This behavior suggests the entanglement of polymer-like structures with a finite molecular weight from the description of "Viscoelastic properties of aqueous surfactant solution" (Toshiyuki Shikata, Surface vol.29, No5 (1991), p399-499). Therefore, although it is not a perfect string-like micelle shape having an infinite molecular weight, it can be inferred that a string-like micelle having a sufficient length to exhibit practically useful viscoelasticity is formed.

In the following standard test (I), the rheology modifier of the present invention preferably observes the rewinding of bubbles in the liquid material when stirring is stopped. The rewinding of bubbles refers to a phenomenon in which the bubbles caught in a liquid substance during stirring move in the direction opposite to the direction of rotation when stirring is stopped in the following standard test (I).
Standard test (I): In a 200 ml beaker, the mass ratio of the water-hard powder to water is water / water-hard powder, and 90 mg of the supernatant liquid collected from the water-hard composition is added to the rheology of the present invention. Add the modifier so that the total content of the components (A) and (B) is 3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the supernatant, and rotate 4 times with a glass rod having a diameter of 6 mm. Stir for 180 seconds per second and observe if there is rewinding of bubbles in the liquid material when stirring is stopped.

The rheology modifier of the present invention can also be used as a pipe friction resistance reducing agent.
The piping friction resistance reducing agent is added to the water in the piping that forms the closed circulation system to suppress the turbulent flow of water, and further reduces the frictional resistance between the piping and water to convey the power of the cold / hot water pump ( An agent that reduces pumping energy).
The matters described in the liquid rheology modifier of the present invention can be appropriately applied to the pipe friction resistance reducing agent.
When the pipe friction reducing agent of the present invention is added to the water of the closed circulation system of the cold / hot water pump, the components (A) and (B) form a string-shaped micelle, and the string-shaped micelle is the energy of the turbulence of the circulating water. It can absorb (turbulent vortices) and change the flow of circulating water from turbulent to laminar. As a result, the friction in the pipe is reduced, so that the transport power of the hot / cold water pump can be reduced.
Further, as the pipe friction reducing agent, those containing a cationic surfactant and an aromatic anion activator have been proposed, and examples thereof include Japanese Patent Application Laid-Open No. 58-185692.

The rheology modifier of the present invention can also be used as a thickening gelling agent.
The matters described in the rheology modifier of the present invention can be appropriately applied to the thickening gelling agent.
The thickening gelling agent of the present invention has high viscoelasticity due to the formation of string-like micelles by the components (A) and (B). Therefore, for example, when added to a cleaning agent composition, it is vertical or inclined. It can be adhered to a dirty surface such as hard surface for a longer period of time, and a high cleaning effect can be obtained.

When the rheology modifier of the present invention is used as a rheology modifier for a hydraulic slurry composition, since it does not contain a cationic surfactant, sand containing clay can also be used, and in a place containing clay. Construction is also possible. Bentonite is widely used as a rheology modifier for building civil engineering, but it can also be used in combination with bentonite.

The present invention provides the use of a mixture containing (A) component, (B) component, (C) component and water as a rheology modifier.
The present invention also provides the use of a mixture containing a component (A), a component (B), a component (C) and water as a rheology modifier.
Further, the present invention is a rheology modifier of a mixture containing (A) component, (B) component, (C) component and water, and a string-shaped micelle formed from (A) component and (B) component. Provide use as.
For these uses or uses, the matters described above, for example, preferred embodiments of the component (A), the component (B), and the component (C) can be appropriately applied.

<Slurry composition>
The slurry composition of the present invention contains the rheology modifier of the present invention, water, and powder. That is, the slurry composition of the present invention contains (A) component, (B) component, (C) component, water, and powder.
As an example of the slurry composition of the present invention, a string-shaped micelle containing (A) component, (B) component, (C) component, water, and powder and formed from (A) component and (B) component. A slurry composition containing the above can be mentioned. When string-shaped micelles are formed, the slurry composition of the present invention is similar to the Maxwell type in the dynamic viscoelasticity of the aqueous solution prepared by the composition of the components (A), (B) and water of the slurry composition. Shows the behavior.
The matters described in the rheology modifier of the present invention can be appropriately applied to the slurry composition of the present invention.

As the powder of the present invention, an inorganic powder can be used within a range that does not affect the effect of the present invention. The inorganic powder is not particularly limited, and examples thereof include the following. Among the inorganic powders, those using the hydraulic powder are the hydraulic slurry compositions.
(1) Hydroxide powders such as cement and plaster (2) Powders with posoran action such as fly ash, silica fume, volcanic ash and silicic acid white clay (3) Latent hydrohardness such as coal ash, blast furnace slag and silicate soil Powder (4) Caolin, aluminum silicate, clay, talc, mica, calcium silicate, sericite, bentonite and other silicates (5) Calcium carbonate, magnesium carbonate, barium carbonate, basic lead carbonate and other carbonates (6) Sulfates such as calcium sulfate and barium sulfate (7) Chromates such as strontium chromate and pigment yellow (8) Molybdenate such as zinc molybdenate, zinc molybdate and magnesium molybdenum (9) Alumina, Metal oxides such as antimony oxide, titanium oxide, cobalt oxide, triiron tetroxide, ferrous trioxide, trilead tetroxide, lead monoxide, chromium green oxide, tungsten trioxide, yttrium oxide (10) aluminum hydroxide, Metal hydroxides such as magnesium hydroxide, calcium hydroxide, iron hydroxide and metatitanic acid (11) Metal carbides such as silicon carbide, tungsten carbide, boron carbide and titanium carbide (12) Aluminum nitride, silicon nitride, boron nitride, Zirconia, barium titanate, satin white, carbon black, graphite, chrome yellow, mercury sulfide, ultramarine, Paris blue, titanium yellow, chrome vermilion, lithopon, copper acetohydrate, nickel, silver, palladium, zircone titanate Other inorganic powders not classified in (1) to (11) above, such as lead acid acid.

Examples of the powder include a water-hard powder or a mixed powder of water-hard powder and bentonite. Examples of the powder include cement or a mixed powder of cement and bentonite.

The slurry composition of the present invention preferably has a total content of the component (A) and the component (B) of 0.1 part by mass or more from the viewpoint of obtaining practically sufficient viscoelasticity with respect to 100 parts by mass of water. , More preferably 0.25 parts by mass or more, still more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and preferably 30 parts by mass or less, more preferably 10 parts by mass or less, still more preferably. It is 8 parts by mass or less, more preferably 6 parts by mass or less, and even more preferably 5 parts by mass or less. The water here is the water in the aqueous phase portion of the slurry composition.
Further, in the slurry composition of the present invention, the content of the component (A) is preferably 0.05 part by mass or more, more preferably 0.05 part by mass or more, from the viewpoint of obtaining practically sufficient viscoelasticity with respect to 100 parts by mass of water. 0.12 parts by mass or more, more preferably 0.25 parts by mass or more, still more preferably 0.5 parts by mass or more, and preferably 5 parts by mass or less, more preferably from the viewpoint of suppressing foaming in the slurry composition. Is 4 parts by mass or less, more preferably 2 parts by mass or less. The water here is the water in the aqueous phase portion of the slurry composition.
Further, in the slurry composition of the present invention, the content of the component (B) is preferably 0.05 part by mass or more, more preferably 0.05 part by mass or more, from the viewpoint of obtaining practically sufficient viscoelasticity with respect to 100 parts by mass of water. 0.12 parts by mass or more, more preferably 0.25 parts by mass or more, still more preferably 0.5 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4 parts by mass or less, still more preferably 2 parts by mass. It is less than a part. The water here is the water in the aqueous phase portion of the slurry composition.
In the slurry composition of the present invention, the total content of the component (A) and the component (B) is within a predetermined range, and the respective contents of the component (A) and the component (B) are within a predetermined range. Is preferable.

Further, in the slurry composition of the present invention, the content of the component (C) is preferably 0.004 part by mass or more, more preferably 0.004 part by mass or more, from the viewpoint of exhibiting viscous elasticity in a wide temperature range with respect to 100 parts by mass of water. 0.008 parts by mass or more, more preferably 0.01 parts by mass or more, even more preferably 0.03 parts by mass or more, and preferably 0.8 parts by mass or less from the viewpoint of maintaining viscoelasticity in a wide temperature range. , More preferably 0.6 parts by mass or less, still more preferably 0.4 parts by mass or less, still more preferably 0.1 parts by mass or less, still more preferably 0.08 parts by mass or less. The water here is the water in the aqueous phase portion of the slurry composition.

Further, the slurry composition of the present invention can contain the component (D). When the component (D) is contained, the content of the component (D) in the slurry composition of the present invention is preferably 0.2 with respect to 100 parts by mass of water from the viewpoint of workability of the rheology modifier. By mass or more, more preferably 0.4 parts by mass or more, further preferably 0.8 parts by mass or more, even more preferably 1.0 part by mass or more, and from the viewpoint of imparting excellent viscoelasticity, preferably 50 parts or more. It is less than or equal to parts by mass, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. The water here is the water in the aqueous phase portion of the slurry composition.

Further, the slurry composition of the present invention can contain the component (E). When the component (E) is contained, the content of the component (E) in the slurry composition of the present invention is such that the rheological effect is exhibited when the slurry composition contains bentonite or clay mineral with respect to 100 parts by mass of water. From the viewpoint, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.2 parts by mass or more, still more preferably 0.3 parts by mass or more, and increasing the slurry composition. From the viewpoint of suppressing stickiness, it is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 5 parts by mass or less. The water here is the water in the aqueous phase portion of the slurry composition.

The slurry composition of the present invention has a water / powder ratio (W / P) of preferably 12% by mass or more, more preferably 30% by mass or more, still more preferably, from the viewpoint of ensuring the fluidity of the slurry composition. 50% by mass or more, more preferably 100% by mass or more, and from the viewpoint of suppressing shrinkage due to drying of the slurry composition, preferably 1000% by mass or less, more preferably 500% by mass or less, still more preferably 300% by mass or less. Is.
Here, the water / powder ratio (W / P) is a mass percentage (mass%) of water and powder in the slurry composition, and is calculated by water / powder × 100.

From the viewpoint of the rheology modifying effect, the viscosity of the slurry composition of the present invention is preferably 50 mPa · s or more, more preferably 100 mPa · s or more, further preferably 500 mPa · s or more, and fluidity at 23 ° C. From the viewpoint of securing, it is 10,000 mPa · s or less. Here, the viscosity of the slurry composition is determined by stirring the slurry composition to be measured using a B-type viscometer (manufactured by RION Co., Ltd., VISCOTESTER VT-04E, rotor No. 1) at a rotation speed of 62.5 rpm. It is a value measured after 1 minute.

<Manufacturing method of slurry composition>
The present invention provides a method for producing a slurry composition in which the rheology modifier, water, and powder of the present invention are mixed.
The items described in the rheology modifier and the slurry composition of the present invention can be appropriately applied to the method for producing the slurry composition of the present invention.

In the method for producing a slurry composition of the present invention, it is preferable to prepare a slurry containing water and powder in advance, add the rheology modifier of the present invention to the slurry, and mix them to produce a slurry composition. ..

The slurry composition and the method for producing a slurry composition of the present invention are excellent in material separation resistance and are useful as the following methods for producing a hydraulic slurry composition and a hydraulic slurry composition.
Since the slurry composition of the present invention has not only viscosity but also high viscoelasticity, it is considered to be excellent in material separation resistance. In other words, it is considered that viscoelasticity is also necessary because the particles of the slurry slowly settle only with high viscosity.

<Hydraulic slurry composition>
The present invention provides a hydraulic slurry composition containing the rheology modifier of the present invention, water, and a hydraulic powder. That is, the hydraulic slurry composition of the present invention contains (A) component, (B) component, (C) component, water, and hydraulic powder.
As an example of the hydraulic slurry composition of the present invention, it contains (A) component, (B) component, (C) component, water, and hydraulic powder, and is formed from (A) component and (B) component. Examples thereof include hydraulic slurry compositions containing string-shaped micelles. When string-shaped micelles are formed, the water-hard slurry composition of the present invention has a Maxwell type dynamic viscoelasticity of an aqueous solution prepared from the components (A), (B) and water of the slurry composition. Shows behavior similar to.

The items described in the rheology modifier, slurry composition, and method for producing a slurry composition of the present invention can be appropriately applied to the hydraulic slurry composition of the present invention.

The hydraulic powder used in the hydraulic slurry composition of the present invention is a powder that hardens when mixed with water, and is, for example, ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, and resistance to water. Sulfate Portland cement, low heat Portland cement, white Portland cement, eco-cement (for example, JIS R5214, etc.) can be mentioned. Among these, cement selected from early-strength Portland cement, ordinary Portland cement, sulfuric acid-resistant Portland cement and white Portland cement is preferable from the viewpoint of shortening the time required to reach the required strength of the hydraulic slurry composition. Strong Portland cement and ordinary Portland cement are more preferable.

Further, the hydraulic powder may include blast furnace slag, fly ash, silica fume, anhydrous gypsum and the like, and may also contain non-hydraulic limestone fine powder and the like. As the water-hard powder, blast furnace cement, fly ash cement, silica fume cement or the like in which cement is mixed with blast furnace slag, fly ash, silica fume or the like may be used.
Further, the hydraulic powder includes cement or a mixed powder of cement and bentonite.

The hydraulic slurry composition of the present invention preferably contains an aggregate. Examples of the aggregate include fine aggregate and coarse aggregate. The fine aggregate is preferably mountain sand, land sand, river sand and crushed sand, and the coarse aggregate is preferably mountain gravel, land gravel, river gravel and crushed stone. Depending on the application, a lightweight aggregate may be used. The term for aggregate is based on "Concrete Overview" (published by Technical Shoin on June 10, 1998).

For the hydraulic slurry composition of the present invention, a dispersant generally used for hydraulic slurries can be used as long as the effects of the present invention are not affected.
When adding the dispersant, it is preferable to knead the water, the powder and the dispersant, and then add the rheology modifier of the present invention and mix them.

In the water-hard slurry composition of the present invention, examples of the dispersant include a naphthalene-based polymer, a polycarboxylic acid-based polymer, a melamine-based polymer, a phenol-based polymer, and a lignin-based polymer. From the viewpoint of shortening the time required to reach the required strength, it is preferably a dispersant selected from a naphthalene-based polymer, a polycarboxylic acid-based polymer, a melamine-based polymer, and a phenol-based polymer, and more preferably a naphthalene-based polymer. It is a dispersant selected from a polymer, a polycarboxylic acid-based polymer, and a phenol-based polymer, and more preferably a polycarboxylic acid-based polymer.

Naphthalene-based polymers include naphthalene sulfonic acid formaldehyde condensate (Mighty 150 manufactured by Kao Co., Ltd.), and melamine-based polymers include melamine sulfonate formaldehyde condensate (for example, Mighty 150-V2 manufactured by Kao Co., Ltd.) and phenolic polymers. The polymer is a phenol sulfonic acid formaldehyde condensate (compounds described in JP-A-49-10419), and the lignin-based polymer is lignin sulfonate (Ultradin NA manufactured by Boregard, Nippon Paper Chemical Co., Ltd.). Sun extract, vanillex, pearllex, etc.) can be used.

As the polycarboxylic acid-based copolymer, a copolymer of a monoester of polyalkylene glycol and (meth) acrylic acid and a carboxylic acid such as (meth) acrylic acid (for example, JP-A-8-12397). Compounds, etc.), copolymers of unsaturated alcohols with polyalkylene glycols and carboxylic acids such as (meth) acrylic acid, copolymers of unsaturated alcohols with polyalkylene glycols and dicarboxylic acids such as maleic acid, etc. Can be used. Here, (meth) acrylic acid means a carboxylic acid selected from acrylic acid and methacrylic acid.

The hydraulic slurry composition may further contain other components as long as it does not affect the effects of the present invention. For example, AE agent, retarder, foaming agent, thickener, foaming agent, waterproofing agent, fluidizing agent, defoaming agent and the like can be mentioned.

The water-hard slurry composition of the present invention preferably has a total content of the component (A) and the component (B) of 0.1 mass by mass from the viewpoint of obtaining practically sufficient viscoelasticity with respect to 100 parts by mass of water. More than parts, more preferably 0.25 parts by mass or more, still more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, and from the viewpoint of not inhibiting the hydration reaction of the water-hard slurry composition. Is 30 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 5 parts by mass or less.
Further, in the water-hard slurry composition of the present invention, the content of the component (A) is preferably 0.05 part by mass or more from the viewpoint of obtaining practically sufficient viscoelasticity with respect to 100 parts by mass of water. It is preferably 0.12 parts by mass or more, more preferably 0.25 parts by mass or more, still more preferably 0.5 parts by mass or more, and preferably 5 parts by mass from the viewpoint of suppressing foaming in the water-hard slurry composition. Hereinafter, it is more preferably 4 parts by mass or less, still more preferably 2 parts by mass or less.
Further, in the water-hard slurry composition of the present invention, the content of the component (B) is preferably 0.05 part by mass or more from the viewpoint of obtaining practically sufficient viscoelasticity with respect to 100 parts by mass of water. It is preferably 0.12 parts by mass or more, more preferably 0.25 parts by mass or more, still more preferably 0.5 parts by mass or more, and from the viewpoint of not inhibiting the hydration reaction of the water-hard slurry composition, it is preferably 5. It is less than or equal to parts by mass, more preferably less than 4 parts by mass, and even more preferably less than 2 parts by mass.
In the hydraulic slurry composition of the present invention, the total content of the component (A) and the component (B) is within a predetermined range, and the respective contents of the component (A) and the component (B) are within a predetermined range. Is preferable. The water here is the water in the aqueous phase portion of the hydraulic slurry composition.

In the hydraulic slurry composition of the present invention, the mass ratio (A) / (B) of the component (A) to the component (B) is preferably 3/97 or more, more preferably 10 from the viewpoint of obtaining high viscoelasticity. / 90 or more, more preferably 20/80 or more, still more preferably 30/70 or more, still more preferably 40/60 or more, and preferably 95/5 or less, more preferably 90/10 or less, still more preferably. It is 80/20 or less, more preferably 70/30 or less, and even more preferably 60/40 or less.

When the water-hard slurry composition of the present invention contains the component (B1) and the component (B2) as the component (B), the mass ratio of the content of the component (B1) to the content of the component (B2) ( B1) / (B2) are preferably 0.5 or more, more preferably 2.0 or more, still more preferably 4.0 or more, and preferably 10.0, from the viewpoint of increasing the viscoelasticity of the slurry at low temperature. Below, it is more preferably 7.0 or less, still more preferably 6.0 or less.

Further, the water-hard slurry composition of the present invention preferably contains 0.004 parts by mass or more of the component (C) from the viewpoint of exhibiting viscous elasticity in a wide temperature range with respect to 100 parts by mass of water. It is preferably 0.008 parts by mass or more, more preferably 0.01 parts by mass or more, even more preferably 0.03 parts by mass or more, and preferably 0.8 parts by mass from the viewpoint of maintaining viscoelasticity in a wide temperature range. Parts or less, more preferably 0.6 parts by mass or less, still more preferably 0.4 parts by mass or less, still more preferably 0.1 parts by mass or less, still more preferably 0.08 parts by mass or less. The water here is the water in the aqueous phase portion of the hydraulic slurry composition.

In the water-hard slurry composition of the present invention, the mass ratio ((A) + (B)) / (C) of the total content of the component (A) and the component (B) to the content of the component (C) is From the viewpoint of developing the viscoelasticity of the slurry in a wide temperature range, it is preferably 6.0 or more, more preferably 8.0 or more, further preferably 10.0 or more, still more preferably 12.0 or more, and It is preferably 200 or less, more preferably 150 or less, still more preferably 125 or less, still more preferably 100 or less, still more preferably 75 or less, still more preferably 50 or less, still more preferably 25 or less.

Further, the hydraulic slurry composition of the present invention can contain the component (D). When the component (D) is contained, the content of the component (D) in the water-hard slurry composition of the present invention is preferably 0 with respect to 100 parts by mass of water from the viewpoint of workability of the rheology modifier. .2 parts by mass or more, more preferably 0.4 parts by mass or more, further preferably 0.8 parts by mass or more, still more preferably 1.0 part by mass or more, and from the viewpoint of imparting excellent viscoelasticity, it is preferable. Is 50 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less. The water here is the water in the aqueous phase portion of the hydraulic slurry composition.

Further, the hydraulic slurry composition of the present invention can contain the component (E). When the powder used in the hydraulic slurry composition of the present invention contains hydraulic powder and bentonite, and further cement and bentonite, the hydraulic slurry composition of the present invention preferably contains the component (E). When the component (E) is contained, the content of the component (E) in the water-hard slurry composition of the present invention is when the water-hard slurry composition contains bentonite and clay minerals with respect to 100 parts by mass of water. From the viewpoint of exhibiting the rheological effect, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.2 parts by mass or more, still more preferably 0.3 parts by mass or more, and water. From the viewpoint of suppressing thickening of the rigid slurry composition, it is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 5 parts by mass. It is less than a part. The water here is the water in the aqueous phase portion of the hydraulic slurry composition.

The hydraulic slurry composition of the present invention preferably has a dispersant content of 0.0005 parts by mass or more, more preferably 0.0005 parts by mass or more, from the viewpoint of obtaining practically sufficient fluidity with respect to 100 parts by mass of the hydraulic powder. Is 0.001 part by mass or more, more preferably 0.005 part by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, from the viewpoint of not inhibiting the hydration reaction of the hydraulic slurry composition. More preferably, it is 3 parts by mass or less.

The water-hard slurry composition of the present invention has a water / water-hard powder ratio (W / C) of preferably 12% by mass or more, more preferably 30% by mass, from the viewpoint of ensuring the fluidity of the water-hard slurry composition. % Or more, more preferably 50% by mass or more, still more preferably 100% by mass or more, and from the viewpoint of ensuring the water hardness of the water-hard slurry composition, preferably 1000% by mass or less, more preferably 500% by mass or less. , More preferably 300% by mass or less, still more preferably 150% by mass or less.
Here, the water / water-hard powder ratio (W / C) is the mass percentage (mass%) of water and the water-hard powder in the water-hard slurry composition, and is calculated by water / water-hard powder × 100. Will be done. The water / hydraulic powder ratio is calculated based on the amount of powder having physical characteristics that hardens by a hydration reaction.
The hydraulic powder is selected from powder having a physical property of being cured by a hydration reaction such as cement, powder having a pozolan action, powder having latent hydraulic property, and stone powder (calcium carbonate powder). When powders are included, in the present invention, those amounts are also included in the amount of hydraulic powder. When the powder having physical properties that are cured by the hydration reaction contains a high-strength admixture, the amount of the high-strength admixture is also included in the amount of the hydraulic powder. This also applies to other mass parts related to the mass of the hydraulic powder.

The viscosity of the hydraulic slurry composition of the present invention is preferably 50 mPa · s or more, more preferably 100 mPa · s or more, further preferably 500 mPa · s or more, and 10 at 23 ° C. from the viewpoint of rheology modifying effect. It is 000 mPa · s or less. Here, the viscosity of the hydraulic slurry composition is determined by rotating the hydraulic slurry composition to be measured at a rotation speed of 62.5 rpm using a B-type viscometer (VISCOTESTER VT-04E, rotor No. 1 manufactured by RION Co., Ltd.). It is a value measured after 1 minute after stirring with.

<Manufacturing method and pumping method of hydraulic slurry composition>
The present invention provides a method for producing a hydraulic slurry composition in which the rheology modifier, water, and hydraulic powder of the present invention are mixed.
The items described in the rheology modifier, slurry composition, slurry composition production method, and water-hard slurry composition of the present invention can be appropriately applied to the method for producing a water-hard slurry composition of the present invention.

In the method for producing a water-hard slurry composition of the present invention, a slurry containing water and water-hard powder is prepared in advance, and the rheology modifier of the present invention is added to the slurry and mixed to form a water-hard slurry composition. It is preferable to manufacture the product.
That is, as a method for producing a water-hard slurry composition of the present invention, a water-hard slurry composition in which a slurry containing water and water-hard powder is prepared, the rheology modifier of the present invention is added to the slurry, and the slurry is mixed. A method of manufacturing a product can be mentioned.

In the method for producing a water-hard slurry composition of the present invention, all existing devices can be used for mixing each component, for example, a tilting mixer, a pan-type mixer, a biaxial forced mixer, an omni mixer, a Henschel mixer, and the like. Examples include a V-type mixer and a nouter mixer.

Examples of the method for placing the hydraulic slurry composition according to the present invention include a method of pumping the hydraulic slurry composition and a step of pumping the hydraulic slurry composition. Be done.

According to the present invention, the hydraulic slurry composition of the present invention is transported to a casting place and then poured into a mold for casting. Examples of the transportation method include generally used methods, and are not particularly limited, and examples thereof include a method of pumping, a method of transporting by a mixer truck, and a method of pouring and moving from a mixer to a hopper. From the viewpoint of reducing viscoelasticity due to shearing force, there is an advantage that even a low-capacity pump can be pumped when placing in a place where it cannot be transported by a mixer truck or a hopper, and the transport method of pumping is particularly preferable.

When the hydraulic slurry composition of the present invention is pumped, it can be carried out by pumping the hydraulic slurry composition adjusted to a desired physical property and kneaded into an appropriately arranged pipe. After being transported by a mixer truck or the like, the hydraulic slurry can be pumped by using a pump such as a pump truck.

The types of pumps include generally used squeeze type and piston type, and are not particularly limited.

<Ingredients used>
The following components were used as the component (A), the component (B), and the component (C).
(A) Component (a-1): Polyoxyethylene alkenyl sulfate ester salt (in general formula (a1), R ^1a : alkenyl group (oleyl group) having 18 carbon atoms, R ^2a : ethylene group, n: 9, M ¹ : Ammonium ion)
(A-2): Polyoxyethylene alkyl sulfate ester salt (in general formula (a1), R ^1a : alkyl group having 18 carbon atoms (stearyl group), R ^2a : ethylene group, n: 9, M ¹ : ammonium ion )
Component (B): Oleic acid diethanolamide (fatty acid diethanolamide which is an alkenyl group (oleyl group) having 18 carbon atoms in the fatty acid portion)
(B-2): Lauric acid diethanolamide (fatty acid diethanolamide which is an alkyl group (lauryl group) having 12 carbon atoms in the fatty acid portion)
(C) Ingredients The compounds shown in Tables 1 and 2 were used.
Component (D) (d-1): Propylene glycol

<Method of preparing rheology modifier>
A rheology modifier was prepared by mixing the components (A), (B), (C), and water having the contents shown in Tables 1 and 2. At that time, an appropriate amount of propylene glycol was used as the component (D) to obtain a one-component rheology modifier. The content in the table is the content of the effective component.
Specifically, 20 ° C. water, (A) component, (C) component, and (D) component are mixed in a screw tube, and the (A) component is completely dissolved in a constant temperature bath (40 ° C.). After confirming that the entire amount of the component (A) was dissolved, the component (B) was blended and stirred until the component (B) was uniformly dispersed. By this method, each rheology modifier shown in Tables 1 and 2 was obtained.
By mixing the rheology modifier of the examples in the table with water and a hydraulic powder, a hydraulic slurry composition having viscoelasticity can be obtained.

<Rheology modification effect of hydraulic slurry composition>
(1) Preparation of hydraulic slurry composition 400 g of water adjusted to the predetermined temperature shown in Tables 1 and 2 and cement (ordinary Portland cement, Taiheiyo Cement and Sumitomo Osaka Cement mixed at a mass ratio of 50/50) 400 g was mixed and stirred for 30 seconds using a commercially available hand mixer. Then, the prepared rheology modifier is added so that the rheology modifier is 4 parts by mass with respect to 100 parts by mass of water in the hydraulic slurry composition, and stirring is continued for 90 seconds to make the rheology modifier hydraulic. A slurry composition was prepared.
The total amount of water initially added to the cement and the amount of water in the rheology modifier was adjusted to be 400 g. Tap water was used as the water.
The water / hydraulic powder ratio (W / C) of each prepared hydraulic composition was 100% by mass.

(2) Measurement of Slurry Viscosity The viscosity of the obtained water-hard slurry composition is stirred using a B-type viscometer (RION Co., Ltd., VISCOTESTER VT-04E, rotor No. 1) at a rotation speed of 62.5 rpm. , The value 1 minute after stirring was adopted. The results are shown in Tables 1 and 2. When the viscosity of the hydraulic slurry composition is 1,000 mPa · s or more, viscoelasticity is confirmed in the slurry, but the higher the viscosity, the higher the modification effect of the hydraulic slurry, which is preferable.

As is clear from the results in the table, the rheology modifier of the example has a wide temperature range of 7 ° C. to 32 ° C., particularly 32, as compared with the rheology modifier of the comparative example containing no component (C). It can be seen that the hydraulic slurry has high viscosity and viscoelasticity even in a high temperature region of ° C., and has a high modification effect on the hydraulic slurry.

Claims (3)

(A) Sulfate ester or salt thereof (hereinafter referred to as component (A)), (B), in which the hydrocarbon group has 12 or more and 22 or less carbon atoms and the average number of moles of alkylene oxide added is 0 or more and 25 or less. Fatty acid alkanolamide (hereinafter referred to as (B) component) , ( C) carboxylic acid having 8 or more carbon atoms or a salt thereof (hereinafter referred to as (C) component) , water having a fatty acid portion having 10 or more and 22 or less carbon atoms. And a slurry composition containing powder. The slurry composition according to claim 1, wherein the component (C) is a monovalent carboxylic acid or a salt thereof. The slurry composition according to claim 1 or 2 , wherein the powder is a water-hard powder or a mixed powder of the water-hard powder and bentonite.