JP6877391B2 - Granular composition and dispersant - Google Patents

Description

The present invention relates to granular compositions and dispersants.

Lignin is a natural macromolecular component present in trees and is generated on a large scale and commercially in the paper industry that uses wood as a raw material. For example, kraft lignin can be obtained from kraft pulp effluent, and lignin sulfonic acid can be obtained from sulfite pulp effluent. Kraft lignin and lignin sulfonic acid, or their processed products, are dyes, hydraulic compositions (eg, cement, gypsum), inorganic and organic pigments, coal-water slurries, pesticides, ceramics, oil field drilling muddy water, etc. as dispersants. It is widely used in a wide range of industrial fields.

Lignin derivatives have been proposed in consideration of application to various uses such as muddy water for oil field drilling (see, for example, Patent Documents 1 and 2). It has been shown that these lignin derivatives have a low viscosity value after a high temperature history and are excellent in thermal properties.

Japanese Unexamined Patent Publication No. 2011-240224 Japanese Unexamined Patent Publication No. 2011-240223

Ligno sulfonic acid is generally known to be inferior in heat resistance. Therefore, when it is used for excavation or cement dispersion under high temperature such as in summer, heat resistance at higher temperature is required and there is room for improvement.

An object of the present invention is to provide a solid substance of a lignin-containing composition which exhibits high dispersibility and excellent heat resistance.

As a result of diligent studies on the above problems, the present inventors have found that the above problems can be solved by including a lignin sulfonic acid compound and a water-soluble compound and defining the thermal weight reduction rate at 50 to 80%. We have found and completed the present invention.
That is, the present inventors provide the following [1] to [11].
[1] A granular composition containing a lignin sulfonic acid-based compound and a water-soluble compound and having a thermogravimetric reduction rate of 50 to 80% as measured by a thermogravimetric differential thermal analyzer.
[2] The granular composition according to the above [1], wherein the thermal decomposition point measured by a thermogravimetric differential thermal analyzer is 350 ° C. or higher and lower than 400 ° C.
[3] The granular composition according to the above [1] or [2], further comprising a lignin derivative which is a reaction product of a lignin sulfonic acid compound and a water-soluble compound.
[4] The granular composition according to any one of the above [1] to [3], wherein the water-soluble compound is an aromatic water-soluble compound.
[5] The granular composition according to the above [3] or [4], wherein the lignin derivative has an anionic functional group.
[6] The granular composition according to any one of [3] to [5] above, wherein the lignin derivative has a polyalkylene oxide chain having an average number of moles of alkylene oxide added of 25 or more.
[7] In the lignin derivative, the reaction weight ratio ([L] / [M]) of the lignin sulfonic acid-based compound [L] and the aromatic water-soluble compound [M] is 1 to 99/99 to 1. The granular composition according to any one of the above [4] to [6].
[8] A group in which the aromatic water-soluble compound comprises an aromatic water-soluble compound having a polyalkylene oxide chain, an aromatic water-soluble compound having a carboxyl group, and an aromatic water-soluble compound having a sulfo group. The granular composition according to any one of the above [4] to [7], which comprises one or more selected from the above.
[9] The granular composition according to any one of the above [4] to [8], which contains a lignin derivative having a reaction rate of the aromatic water-soluble compound of 50% or more.
[10] A dispersant containing the granular composition according to any one of the above [1] to [9].
[11] The dispersant according to the above [10], which is a muddy water dispersant for oil field excavation or a dispersant for a hydraulic composition.

According to the present invention, it is possible to provide a solid substance of a lignin-containing composition showing high dispersibility and excellent heat resistance.

Hereinafter, the present invention will be described in detail according to the preferred embodiment thereof. In this specification, the notation "AA to BB" means AA or more and BB or less. The thermogravimetric differential thermal analyzer is also referred to as "TG-DTA".

[1. Granular composition]
The granular composition of the present invention contains a lignin sulfonic acid-based compound and a water-soluble compound, and has a thermogravimetric reduction rate of 50 to 80% as measured by TG-DTA. Further, the granular composition of the present invention preferably has a thermal decomposition point of 350 ° C. or higher and lower than 400 ° C. by TG-DTA.

[1-1. Physical characteristics]
In the granular composition of the present invention, the lower limit of the thermogravimetric reduction rate measured by TG-DTA is 50% or more, preferably 55% or more, and more preferably 60% or more. When it is 50% or more, the amount of ash is low, the inhibitory action of unavoidable impurities other than the lignin derivative on the dispersant can be suppressed, and high dispersibility can be ensured. The upper limit thereof is 80% or less, preferably 75% or less, and more preferably 70% or less. When it is 80% or less, heat resistance can be ensured. Therefore, the thermogravimetric reduction rate measured by TG-DTA is 50 to 80%, preferably 55 to 75%, and more preferably 60 to 70%.

In the granular composition of the present invention, the lower limit of the thermal decomposition point measured by TG-DTA is preferably 350 ° C. or higher, more preferably 360 ° C. or higher, still more preferably 370 ° C. or higher. When the temperature is 350 ° C. or higher, heat resistance can be ensured. The upper limit thereof is less than 400 ° C., preferably 398 ° C. or lower, and more preferably 396 ° C. or lower. When the temperature is lower than 400 ° C., the granular composition can be suppressed from being resinified and can function as a dispersant or a binder. Therefore, the thermal decomposition point measured by TG-DTA is preferably 350 ° C. or higher and lower than 400 ° C., more preferably 360 to 398 ° C., and further preferably 370 to 396 ° C.

The thermal decomposition point and the thermal weight reduction rate measured by TG-DTA are values measured using a thermogravimetric differential thermal analyzer (TG-DTA) (trade name "STA7200", manufactured by SII). ..
More specifically, it is a value measured by the following procedure. 10 g of the granular composition is dried and solidified. The method of drying and solidifying is 1) a method of drying and solidifying at 105 ° C for one day with a dryer (trade name "Blower constant temperature incubator DKM600", manufactured by Yamato Scientific Co., Ltd.), and 2) a freeze dryer (trade name "FDU-"). 1200 ”, manufactured by Tokyo Rika Kikai Co., Ltd.) to dry and solidify at -20 ° C for one day, 3) dry and solidify at 180 ° C using a spray dryer (trade name“ TR120 ”, manufactured by Pris). .. Then, about 10 mg of the solidified sample is heated from 50 ° C. to 600 ° C. at a heating rate of 10 ° C./min under a nitrogen atmosphere. The temperature at which the weight loss rate of the sample is maximum is defined as the thermal decomposition point, and the weight loss rate up to 600 ° C. is defined as the thermogravimetric loss rate. The measurement is performed three times for each sample, and the average value is used.

The pyrolysis point and the thermogravimetric reduction rate measured by TG-DTA can be adjusted by appropriately adjusting the types and amounts of the lignin sulfonic acid-based compound, the water-soluble compound, and the lignin derivative. In particular, when a lignin derivative is contained, the reaction conditions of the lignin derivative can be adjusted by appropriately designing. More specifically, the type and amount of the reaction initiator, the concentration of the reaction solution, the ratio of the lignin sulfonic acid compound to the water-soluble compound, the type and amount of the side chain functional group of the water-soluble compound, the reaction temperature, the reaction time, etc. It can be adjusted by changing the proper declaration.

[1-2. Lignin sulfonic acid compound]
The lignin sulfonic acid-based compound is a compound having a skeleton in which the carbon at the α-position of the side chain of the hydroxyphenyl propane structure of lignin is cleaved and a sulfo group (sulfonic acid group) is introduced. The structure of the skeleton portion is shown in Equation (1).

The lignin sulfonic acid-based compound may be a modified product of a compound having a skeleton represented by the above formula (1) (hereinafter, also referred to as “modified lignin sulfonic acid-based compound”). The modification method is not particularly limited, but a method for chemically modifying such as hydrolysis, alkylation, alkoxylation, sulfonate, sulfonic acid esterification, sulfomethylation, aminomethylation, and desulfonatement; lignin sulfonic acid compounds are limited. An example is a method of fractionating the molecular weight by external filtration. Of these, as the chemical modification method, one or more modification methods selected from hydrolysis, alkoxylation, desulfonation and alkylation are preferable.

The lignin sulfonic acid-based compound can take the form of a salt. Examples of the salt include a monovalent metal salt, a divalent metal salt, an ammonium salt, and an organic ammonium salt. Among these, calcium salt, magnesium salt, sodium salt, calcium / sodium mixed salt and the like are preferable.

The method and origin of the lignin sulfonic acid-based compound are not particularly limited, and either a natural product or a synthetic product may be used. The lignin sulfonic acid-based compound is one of the main components of the waste liquid of sulfite pulp obtained by evaporating wood under acidic conditions. Therefore, a lignin sulfonic acid-based compound derived from sulfite pulp waste liquid may be used.

Since lignin sulfonic acid-based compounds (modified lignin sulfonic acid-based compounds) are abundantly contained in commercially available products, such commercially available products may be used in the present invention. Examples of commercially available products include Vanillex HW (manufactured by Nippon Paper Industries), Sun Extract M (manufactured by Nippon Paper Industries), Pearllex NP (manufactured by Nippon Paper Industries), and Sunflow RH (manufactured by Nippon Paper Industries).

Lignin sulfonic acid compounds usually have at least one functional group moiety capable of reacting with a water-soluble compound. Examples of such a moiety include a carboxyl group, a hydroxyl group (phenolic hydroxyl group, alcoholic hydroxyl group), a thiol group, a sulfo group, an aromatic ring, an ether bond, and an alkyl chain.

[1-3. Water-soluble compound]
The water-soluble compound means a compound exhibiting water solubility. Examples of the water-soluble compound include an aromatic water-soluble compound having at least one aromatic skeleton and a known (co) polymer as a cement dispersant. Among them, the water-soluble compound is preferably an aromatic water-soluble compound having at least one aromatic skeleton. The aromatic water-soluble compound is preferably a sulfite pulp waste liquid, that is, a compound capable of reacting with the main component of the sulfite pulp waste liquid, and functional groups contained in the lignin sulfonic acid-based compound (for example, phenolic hydroxyl group, alcoholic hydroxyl group, carboxyl group). , A thiol group) and a compound capable of binding by a chemical reaction are preferable. The form of the chemical reaction is not particularly limited, and radical reactions, ionic bonds, coordination bonds, condensation reactions, reactions involving hydrolysis, reactions involving dehydration, reactions involving oxidation, reactions involving reduction, and reactions involving neutralization are included. Illustrated.

The aromatic water-soluble compound preferably has at least one polar group. This makes it easier to control the physical characteristics of the granular composition, and when it is reacted with a lignin sulfonic acid-based compound, the reactivity becomes good. The polar group may be an ionic functional group. Examples of the polar group include functional groups such as a carboxyl group, a hydroxyl group, a sulfo group, a nitroxyl group, a carbonyl group, a phosphoric acid group, an amino group and an epoxy group. The aromatic water-soluble compound may be used alone or in combination of two or more.

Examples of the aromatic water-soluble compound include the following [A] to [D]. The aromatic water-soluble compound is preferably at least one selected from [A] to [C], and more preferably only [A] or a combination of [A] and [B] and / or [C].

([A] Aromatic water-soluble compound having a polyalkylene oxide chain)
The number of carbon atoms of the alkylene oxide unit constituting the polyalkylene oxide chain (group) is not particularly limited, and is usually 2 to 18, preferably 2 to 4, and more preferably 2 to 3. Examples of the alkylene oxide unit include ethylene oxide unit, propylene oxide unit, and butylene oxide unit. Of these, ethylene oxide units or propylene oxide units are preferable.
The average number of moles of alkylene oxide units added is preferably 25 or more, more preferably 30 or more, and even more preferably 35 or more. Thereby, the dispersibility can be improved. The upper limit is preferably 300 or less, more preferably 200 or less, and even more preferably 150 or less. As a result, the decrease in dispersion retention can be suppressed. Therefore, the average number of moles added is preferably 25 to 300, more preferably 30 to 200, and even more preferably 35 to 150. The above-mentioned average number of moles added is a guideline, and regardless of whether or not the above-mentioned range is satisfied, [A] has a substance (monoalkylene oxide group) to which the alkylene oxide unit is not repeatedly added. You may.

The polyalkylene oxide chain may be composed of one type alone or two or more types of alkylene oxide groups. The addition form of each alkylene oxide group of the polyalkylene oxide chain composed of two or more kinds of alkylene oxide groups may be random, block or a mixture thereof. The terminal unit of the polyalkylene oxide chain is usually a hydroxyl group, but is not limited to this, and may be an alkyl ether or a carboxylic acid ester as long as it does not interfere with the bond with the lignin sulfonic acid compound.

Examples of [A] include oxyalkylene group adducts to aromatic compounds such as phenol, cresol, nonylphenol, naphthol, methylnaphthol, butylnaphthol, bisphenol A, and bisphenol S. More specifically, polyalkylene oxide alkyl phenyl ethers, polyalkylene oxide phenyl ethers, polyalkylene oxide alkyl naphthyl ethers, polyalkylene oxide naphthyl ethers and the like can be mentioned. Among these, benzene ring derivatives are preferable because cocondensability can be good, and at least one of polyalkylene oxide alkyl phenyl ethers and polyalkylene oxide phenyl ethers is more preferable, and polyalkylene oxide phenyl ethers (among others, among them). Additions of oxyalkylene groups to phenol) (eg, preferred ranges of average molar additions of poly (ethylene oxide) monophenyl ethers, poly (propylene oxide) monophenyl ethers, ethylene oxide units and propylene oxide units are as described above). preferable. [A] may be one type or a combination of two or more types.

([B] Aromatic water-soluble compound having a carboxyl group)
[B] includes, for example, a naphthalene ring or a benzene ring derivative having at least one carboxyl group. More specifically, isophthalic acid, oxynaphthoic acid, benzoic acid, hydroxybenzoic acid, and isomers thereof can be mentioned. O-Hydroxybenzoic acid, m-hydroxybenzoic acid, and p-hydroxybenzoic acid are preferable because of their good reactivity. [B] may be one type or a combination of two or more types.

([C] Aromatic water-soluble compound having a sulfo group)
Examples of [C] include alkylnaphthalene sulfonic acid, alkylphenol sulfonic acid, aniline sulfonic acid, and alkylbenzene sulfonic acid. More specifically, naphthalene sulfonic acid, methyl naphthalene sulfonic acid, butyl naphthalene sulfonic acid, phenol sulfonic acid, cresol sulfonic acid, aniline sulfonic acid, benzene sulfonic acid, toluene sulfonic acid, isomers and condensates thereof can be mentioned. Examples of the condensate include a naphthalene sulfonic acid formaldehyde condensate. Since the reactivity is good, a phenol derivative having a sulfo group and aniline sulfonic acid are preferable, and phenol sulfonic acid and aniline sulfonic acid are more preferable. [C] may be one type or a combination of two or more types.

([D] Other aromatic water-soluble compounds)
Examples of [D] include aromatic water-soluble compounds other than [A] to [C], and examples thereof include (alkyl) phenols such as phenol and cresol. [D] may be one type or a combination of two or more types.

(Known (co) polymer)
Known (co) polymers include, for example, a polymer derived from a (poly) alkylene glycol alkenyl ether-based monomer; a water-soluble polyalkylene glycol in which both terminal groups are hydrogen atoms; a polyoxyalkylene structural unit, poly. Examples thereof include copolymers having at least two structural units selected from the group consisting of carboxylic acid structural units and polyester structural units (for example, WO 2018/56124).

[1-4. [E] Other aromatic compounds]
The granular composition of the present invention may contain [E] other aromatic compounds in addition to the above-mentioned lignin sulfonic acid-based compound and water-soluble compound. Examples of [E] include simple aromatic hydrocarbon compounds such as benzene and naphthalene. [E] may be one type or a combination of two or more types.

When the granular composition of the present invention does not contain a lignin derivative, the weight ratio of the lignin sulfonic acid compound ([L]), the water-soluble compound ([M]), and other aromatic compounds ([E]) ([ L]: [M]: [E]) is preferably 30 to 90:10 to 70: 0 to 5, more preferably 40 to 85: 15 to 60: 0 to 3, and 50 to 80:20 to 50: 0 to 2 is more preferable.

[1-5. Lignin derivative]
The granular composition of the present invention preferably further contains a lignin derivative which is a reaction product of a lignin sulfonic acid-based compound and a water-soluble compound. A lignin derivative is usually a polymer containing a structural unit derived from a lignin sulfonic acid-based compound and a structural unit derived from a water-soluble compound. In addition, the lignin derivative may contain a structural unit derived from another aromatic compound.
It is difficult to uniformly specify the chemical structure of a lignin derivative by a general formula or the like. The reason is that lignin, which is the skeleton of the lignin sulfonic acid-based compound constituting the lignin derivative, has a very complicated molecular structure.

The lignin derivative preferably has an anionic functional group and / or a polyalkylene oxide chain in its molecule. Thereby, the dispersibility of the dispersant can be further improved.

The anionic functional group means a functional group in the form of an anion in water, and examples thereof include a hydroxyl group, a carboxyl group, a sulfo group, a phosphoric acid group, and a phenolic hydroxyl group. Among these, a carboxyl group and a sulfo group are preferable.

The anionic functional group may be contained in a structural unit derived from a water-soluble compound or a part of a structural unit derived from a lignin sulfonic acid compound among lignin derivatives, or both of them. It may be included.
The anionic functional group in the lignin derivative can be observed quantitatively and qualitatively by instrumental analysis such as NMR and IR.

The lignin derivative preferably has a polyalkylene oxide chain in its molecule. The number of carbon atoms of the alkylene oxide unit constituting the polyalkylene oxide chain is not particularly limited, and is usually 2 to 18, preferably 2 to 4, and more preferably 2 to 3. Examples of the alkylene oxide unit include ethylene oxide unit, propylene oxide unit, and butylene oxide unit. Of these, ethylene oxide units or propylene oxide units are preferable.

The average number of moles of alkylene oxide units added is preferably 25 or more, more preferably 30 or more, and even more preferably 35 or more. Thereby, the dispersibility can be improved. The upper limit is preferably 300 or less, more preferably 200 or less, and even more preferably 150 or less. As a result, the decrease in dispersion retention can be suppressed. Therefore, the average number of moles added is preferably 25 to 300, more preferably 30 to 200, and even more preferably 35 to 150.

The polyalkylene oxide chain may be contained in a part of the structural units derived from the lignin sulfonic acid compound among the lignin derivatives, or may be contained in the structural units derived from the water-soluble compound, or both. It may be contained in, and it is preferable that it is contained in the latter.
The polyalkylene oxide chain in the lignin derivative can be observed quantitatively and qualitatively by instrumental analysis such as NMR and IR.

(Preparation of lignin derivative)
The lignin derivative may be prepared by reacting a lignin sulfonic acid compound, a water-soluble compound, and if necessary, another aromatic compound. For example, a method of chemically bonding a lignin sulfonic acid-based compound and a water-soluble compound (functional groups (for example, phenolic hydroxyl group, alcoholic hydroxyl group, carboxyl group, thiol group) in the lignin sulfonic acid-based compound) and water-soluble Examples thereof include a method of binding a functional group in a compound, or a method of reacting an aromatic skeleton portion of a lignin sulfonic acid-based compound with a water-soluble compound or another aromatic compound).

As the lignin sulfonic acid-based compound used as a raw material in the preparation of the lignin derivative, a processed powder product that has undergone a treatment such as a powder drying treatment may be used. Being in powder form makes it easy to handle.

From the viewpoint of reactivity, the water-soluble compound is preferably an aromatic water-soluble compound having at least one aromatic skeleton, and more preferably an aromatic water-soluble compound having at least one polar group. One or more selected from the group consisting of ~ [C] is more preferable, and only [A] or a combination of [A] and [B] and / or [C] is even more preferable.
Hereinafter, a case where an aromatic water-soluble compound is used as the water-soluble compound will be described as an example.

Methods for chemically bonding a lignin sulfonic acid compound and an aromatic water-soluble compound include a method of condensing an aromatic water-soluble compound with a lignin sulfonic acid compound (for example, formaldehyde condensation), a radical reaction, and an ion. Binding is exemplified. More specifically, a method of adding formaldehyde to a lignin sulfonic acid-based compound and binding it to an aromatic water-soluble compound; hydrogen radicals were extracted and generated by allowing a radical initiator to act on the lignin sulfonic acid-based compound. Examples thereof include a method of radically reacting a radical with at least one aromatic water-soluble compound.

The reaction temperature may be appropriately set depending on the solvent used, and is not particularly limited, but is usually 0 to 200 ° C, preferably 45 to 150 ° C. When a compound having a low boiling point is used as the reaction solvent, it is preferable to carry out the reaction under pressure using an autoclave in order to improve the reaction rate.

When reacting an aromatic water-soluble compound with a lignin sulfonic acid-based compound, either a solution reaction or a massive reaction can be taken. In the case of a solution reaction, a solvent may be used. Examples of the solvent include water; alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as cyclohexane and n-hexane; esters such as ethyl acetate. Kind: Ketones such as acetone and methyl ethyl ketone; Cyclic ethers such as tetrahydrofuran and dioxane can be mentioned. Above all, it is preferable to use at least one of water and lower alcohol, and it is more preferable to use water. As a result, the solubility of the raw material monomer and the obtained copolymer and the desolvation step can be omitted.
The solvent may be used alone or in combination of two or more (for example, a water-alcohol mixed solvent).

An antifoaming agent may be used when preparing the lignin derivative. As a result, foaming during the reaction can be suppressed, and a uniform reaction system can be constructed.

In the preparation of the lignin derivative, it is preferable that the reaction proceeds stably. Therefore, when the reaction is carried out by solution polymerization, the dissolved oxygen concentration of the solvent used at 25 ° C. is preferably 5 ppm or less, more preferably 0.01 to 4 ppm, still more preferably 0.01 to 2 ppm, still more preferably. Can be adjusted in the range of 0.01 to 1 ppm. The dissolved oxygen concentration may be adjusted in the reaction vessel or may be adjusted in advance before the reaction.

The progress of the reaction is characterized by a clear increase in viscosity. When the desired viscosity is reached, the reaction may be stopped by cooling or neutralization.

In the preparation of the lignin derivative, the addition of water may be adjusted to control the condensation viscosity and the condensation time. Further, the pH during the reaction may be adjusted to an appropriate value. The reaction is usually carried out under acidic conditions. When the reaction system is already acidic due to the aromatic compound having a sulfo group and the unreacted acid contained therein, the reaction may be carried out in the acidic region as it is. If the reaction system is not acidic, an acid catalyst such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, or p-toluenesulfonic acid may be added in advance to bring the pH to 2 or less. The preferred acid is sulfuric acid, but is not limited to the above specific examples.

The reaction weight ratio ([L] / [M]) of the lignin sulfonic acid-based compound [L] constituting the lignin derivative and the aromatic water-soluble compound [M] is not particularly limited, but is preferably 99 to 1. / 1 to 99 (% by weight), more preferably 90 to 2/10 to 98 (% by weight), and even more preferably 70 to 5/30 to 95 (% by weight). When the ratio of the aromatic water-soluble compound [M] is 1.0% by weight or more, the obtained lignin derivative can exhibit the performance originally possessed by the lignin skeleton, that is, the effect of improving the dispersibility. On the other hand, when the ratio of the aromatic water-soluble compound [M] is 99% by weight or less, the molecular weight is in an appropriate range, the cohesiveness is suppressed, and the dispersion performance can be exhibited.
[L] / [M] is defined by (weight of solid content of lignin sulfonic acid-based compound before reaction) / (weight of solid content of aromatic water-soluble compound before reaction), and this method is also used in Examples described later. It is measured at.

The reaction rate of the aromatic water-soluble compound is preferably 50% or more, more preferably 60% or more, and further preferably 70% or more. When the reaction rate is 50% or more, the dispersibility of the obtained lignin derivative can be satisfactorily exhibited.
The reaction rate of the aromatic water-soluble compound can be measured as follows, and is also measured by this method in Examples described later. First, in gel permeation chromatography (GPC) measurement, the peak areas before and after the reaction when UV (detection wavelength 280 nm) is used are compared. Next, when the peak area before the reaction is [b] and the peak area after the reaction is [a], the reaction rate can be calculated by the formula: ([b]-[a]) / [b].

The reaction weight ratio of the components (aromatic water-soluble compound and other aromatic compounds) other than the lignin sulfonic acid-based compound used in the preparation of the lignin derivative is not particularly limited, but the following reaction weight ratio is preferable. [A]: [B]: [C]: ([D] + [E]) = 50 to 100% by weight: 0 to 50% by weight: 0 to 50% by weight: 0 to 10% by weight. Is preferable. However, [A] + [B] + [C] + [D] + [E] = 100% by weight.
Here, [A] to [E] correspond to the above-mentioned compounds.

After completion of the condensation reaction, the reaction solution is preferably subjected to post-treatment with heat at a temperature of 60 to 120 ° C. under a pH condition of 8.0 to 13.0. Post-treatment with heat is usually carried out continuously for 10 minutes to 3 hours. This can significantly reduce the aldehyde content (eg, formaldehyde content) of the reaction solution. In addition to or in place of the removal of free formaldehyde by the so-called Cannizzaro reaction described above, of course, other methods known in the field of chemistry of melamine-formaldehyde resins and phenol-formaldehyde resins, for example, to reduce excess formaldehyde. You may go. Examples of such a method include addition of a formaldehyde absorber (addition of a small amount of sodium bisulfite, addition of hydrogen peroxide).

The pH of the reaction solution may be adjusted to 1.0-4.0, preferably 1.5-2.0, whereby the reaction product may be precipitated as a solid and precipitated at the bottom of the reaction vessel. In this case, the salt aqueous solution of the supernatant is then separated and removed. Then, the remaining mostly salt-free free reaction product can be re-dissolved in water in an amount such that a desired solid concentration can be obtained to obtain a lignin derivative.

For neutralization, a neutralizing agent capable of neutralizing the reaction product and the catalyst may be used. Examples of the neutralizing agent include basic compounds (including salts and hydroxides thereof). More specifically, basic compounds such as sodium hydroxide, calcium hydroxide and Ba (OH) _{2 can be mentioned.} As a result, low-soluble calcium sulfate and barium sulfate are formed together with free sulfuric acid and precipitate in the form of gypsum or the like. Therefore, the precipitate can be separated and removed by subsequent filtration, and a salt-free polymer can be obtained. In addition, unwanted sodium sulfate may be separated and removed by dialysis or ultrafiltration.

If by-products such as sodium sulfate, calcium sulfate, and their hydrates are generated during the addition and neutralization of the basic compound, the basic compound is added in the warmed state after the reaction to bring the warmed state. It is preferable to improve the removability of the by-product by keeping it. The heating is preferably to 40 ° C. or higher. The holding time in the warmed state is preferably 30 minutes or more.

The lignin derivative may be any reaction product obtained by the above-mentioned reaction, and may be either a free acid or a neutralized salt thereof. Neutralizing salts are preferred because the polymer is easy to store and use. Examples of the neutralizing salt of the reaction product include alkali metal salts such as sodium salt or potassium salt; alkaline earth metal salts such as calcium salt; ammonium salt; and organic amine salt.
After the reaction is completed, the concentration of the obtained lignin derivative may be adjusted, if necessary.

(Physical characteristics of lignin derivative)
The weight average molecular weight of the lignin derivative is not particularly limited, but is preferably 1,000 to 500,000, more preferably 2,000 to 300,000, and even more preferably 5,000 to 100. It is 000. The weight average molecular weight can be measured by a known method of converting to polyethylene glycol by gel permeation chromatography (GPC).

The measurement conditions for GPC are as follows.
Measuring device; Column used by Tosoh; Shodex Volume OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ
Eluent; 0.05 mM sodium nitrate / acetonitrile 8/2 (v / v)
Standard substance: Polyethylene glycol (manufactured by Tosoh or GL Science)
Detector; differential refractometer (manufactured by Tosoh)

[1-6. Optional ingredient]
The granular composition of the present invention may contain an optional component in addition to the above, as long as the effects of the present invention are not impaired. Optional components include water-hard composition dispersants (eg, cement dispersants, sol dispersants), oil field drilling muddy water dispersants, dye dispersants, chelating agents, cleaning agents, coagulants, thickeners, coating agents, etc. Examples include paints, adhesives, and water-absorbent resins.

[1-7. Method for producing granular composition]
The granular composition of the present invention may be produced by (1) separately blending a lignin sulfonic acid-based compound and a water-soluble compound and then drying the granular composition, or (2) the lignin sulfonic acid-based compound and the water-soluble compound. It can also be produced by preparing a lignin derivative which is a reaction product with and drying the lignin derivative. When preparing a lignin derivative, a lignin sulfonic acid-based compound and a water-soluble compound may be further added to the prepared lignin derivative. The preparation of the lignin derivative is as described above. Hereinafter, the drying method will be described.

As a drying method, for example, a method of neutralizing with a hydroxide of a divalent metal such as calcium or magnesium to obtain a polyvalent metal salt and then drying; supporting the material on an inorganic powder such as silica-based fine powder and drying. Method; A method of drying and solidifying in a thin film on a support of a drying device (for example, a drum type drying device, a disk type drying device or a belt type drying device); a method of drying and solidifying with a spray dryer.

[2. Dispersant]
The dispersant of the present invention contains the above-mentioned granular composition and can be used for various purposes. For example, dispersants for water-hard composition (for example, dispersants for cement, dispersants for gypsum), muddy water dispersants for oil field excavation, dispersants for dyes, chelating agents, cleaning agents, coagulants, thickeners, coating agents. , Paints, adhesives, water-absorbent resins. The granular composition of the present invention exhibits high dispersibility and excellent heat resistance. Therefore, a muddy water dispersant for oil field excavation or a dispersant for a hydraulic composition is preferable.

[2-1. Muddy water dispersant for oil field drilling]
The dispersant of the present invention can be used as a muddy water dispersant for oil field drilling. The muddy water for oil field excavation may be any muddy water used as a fluid circulating in the well during oil field excavation work and / or recovery work, and its composition is not particularly limited. Oil field drilling muddy water is usually classified into water-based and oil-based, but water-based muddy water is preferable. Aqueous muddy water usually contains clay.
Examples of clay include montmorillonite and bentonite. Of these, bentonite is preferable.

The pH of the muddy water for oil field excavation is not particularly limited, but is preferably 9 to 13, more preferably 9.5 to 11.5, and further preferably around 11. The temperature of the muddy water for oil field excavation is not particularly limited, and may be a high temperature (for example, 80 ° C. or higher, preferably 90 ° C. or higher). The amount of the dispersant of the present invention added to the oil field excavation muddy water is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, based on the weight of the clay in the muddy water. The upper limit is preferably 30% by weight or less, more preferably 20% by weight or less.

[2-2. Dispersant for hydraulic composition]
The dispersant of the present invention can also be used as a dispersant for hydraulic compositions. Hereinafter, the usage pattern will be described.

Examples of the dispersant include various hydraulic materials. The hydraulic material is classified into a cement composition such as cement and gypsum, and other hydraulic materials, but any of them may be used. The dispersant of the present invention can form a hydraulic composition together with the above hydraulic material and water as a dispersant for a hydraulic composition. The hydraulic composition may further contain fine aggregate (sand, etc.) and coarse aggregate (crushed stone, etc.), if desired. Examples of the hydraulic material include cement paste, mortar, concrete and plaster.

[2-2-1. Cement composition]
Among the hydraulic compositions, the cement composition using cement as the hydraulic material (composition containing the dispersant, cement and water of the present invention as essential components) is the most common, and is one of the preferred embodiments. It is one. Hereinafter, the case where the hydraulic composition contains cement (cement dispersant) will be described.

The cement that can be used in the cement composition is not particularly limited, and specific examples thereof include the following.
Portoland cement (normal, fast-strength, super-fast-strength, moderate heat, sulfate-resistant and each low-alkali form); various mixed cements (blast furnace cement, silica cement, fly ash cement); white Portorand cement; alumina cement; ultra-fast hardening Cement (1 clinker fast-hardening cement, 2 clinker fast-hardening cement, magnesium phosphate cement); grout cement; oil well cement; low heat-generating cement (low-heat-generating blast furnace cement, fly ash mixed low-heat-generating blast furnace cement, high content of belite Cement); Ultra-high strength cement; Cement-based solidifying material; Eco-cement (cement manufactured from one or more of municipal waste incineration ash and sewage sludge incineration ash).

Ingredients other than the above cement may be added to the cement composition. Examples of such components include the following.
Fine powder (blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, limestone powder, etc.); gypsum; aggregate (gravel, crushed stone, granulated slag, recycled aggregate, silica stone, clay) Quality, slag, high alumina, silicon carbide, graphite, chrome, chromemag, magnesia, etc. refractory aggregates, etc.).

^{The unit water amount per 1 m 3 of the} cement composition, the amount of cement used, and the water / cement ratio (weight ratio) are not particularly limited, and can be widely used from poor to rich compounds.
The unit water amount is preferably 100 to 185 kg / m ³ , and more preferably 120 to 175 kg / m ³ .
The amount of cement used is preferably 200 to 800 kg / m ³ , and more preferably 250 to 800 kg / m ³ .
The water / cement ratio (weight ratio) is preferably 0.15 to 0.7, more preferably 0.25 to 0.65.

The dispersant of the present invention may be used in a cement composition having a high water reduction rate region, that is, a region having a low water / cement ratio (weight ratio) (for example, 0.15 to 0.5). Furthermore, it is effective for both high-strength concrete with a large amount of unit cement and a small water / cement ratio, and ^{poorly mixed concrete with a small amount of cement used (amount of unit cement) (for example, about 300 kg / m 3 or less).} ..

In a cement composition (for example, when used for mortar or concrete using hydrohard cement), the lower limit of the blending amount of the dispersant of the present invention is preferably 0. It is 01% by weight or more, more preferably 0.02% by weight or more, and further preferably 0.05% by weight or more. When the blending amount is 0.01% by weight or more, the dispersion performance can be sufficiently exhibited. The upper limit thereof is preferably 10.0% by weight or less, more preferably 7.0% by weight or less, and further preferably 5.0% by weight or less. If it is 10.0% by weight or less, the effect of improving dispersibility is not substantially saturated and may be economically advantageous, and adverse effects on various properties of mortar and concrete such as curing delay and strength reduction are adversely affected. Can be suppressed.
Therefore, the blending amount of the dispersant of the present invention is preferably 0.01 to 10.0% by weight, more preferably 0.02 to 7.0% by weight, still more preferably, based on the weight of the cement. Is 0.05 to 5.0% by weight. Such a blending amount brings about various preferable effects such as reduction of unit water amount, increase of strength, and improvement of durability.

The cement composition can exhibit high dispersibility and dispersion retention performance even in a high water reduction rate region. Further, even at a low temperature, sufficient initial dispersibility and viscosity reduction property can be exhibited, and excellent workability can be obtained. Therefore, the cement composition is effective as a raw material for various concretes by being cured.
Examples of concrete include ready-mixed concrete, concrete for secondary concrete products (precast concrete), centrifugal forming concrete, vibration compaction concrete, steam curing concrete, and sprayed concrete. Furthermore, high flow of medium-fluidity concrete (concrete with a slump value of 22 to 25 cm), high-fluidity concrete (concrete with a slump value of 25 cm or more and a slump flow value of 50 to 70 cm), self-filling concrete, self-leveling material, etc. Mortar or concrete that requires sex is also included.

[2-2-2. Gypsum composition]
A gypsum composition using gypsum as a water-hardening material (a composition containing the dispersant, gypsum and water of the present invention as essential components) is also common, and is one of the preferred embodiments of the present invention. Hereinafter, a case where the hydraulic composition contains gypsum (dispersant for gypsum) will be described.

Gypsum is not particularly limited as long as mineral composed mainly of calcium sulfate (CaSO _4), for example, calcium sulfate hemihydrate _{(CaSO 4 · 1 / 2H 2} O: hemihydrate gypsum), calcium sulphate dihydrate _(CaSO 4 · _2H 2 O: gypsum), anhydrous calcium sulfate (CaSO _4: anhydrite) and the like. Common gypsum is semi-hydrated gypsum. The gypsum may be either natural gypsum or chemical gypsum. The origin and properties of natural gypsum are not limited. Examples of chemical gypsum include phosphoric acid gypsum, flue gas desulfurization gypsum, titanium gypsum, wrought gypsum, and hydrofluoric acid gypsum.

In the gypsum composition, the blending amount of the dispersant of the present invention is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, based on the weight of gypsum in terms of solid content. More preferably, it is 0.10% by weight or more. When the blending amount is 0.01% by weight or more, a predetermined dispersibility is exhibited. The upper limit thereof is preferably 5.00% by weight or less, more preferably 3.00% by weight or less, and further preferably 1.00% by weight or less. When it is 5.00% by weight or less, it does not cause a delay in hydration of gypsum, that is, a delay in curing of gypsum, and therefore functions as a dispersant having excellent workability.
Therefore, the blending amount of the dispersant of the present invention is preferably 0.01 to 5.00% by weight, more preferably 0.05 to 3.00% by weight, still more preferably, based on the weight of the gypsum. Is 0.10 to 1.00% by weight. Such a blending amount brings about various preferable effects such as reduction of unit water amount, increase of strength, and improvement of durability.

The content of water in the gypsum composition can be appropriately determined, and is usually 20% by weight or more, preferably 40% by weight or more, based on the weight of gypsum. The upper limit is usually 150% by weight or less, preferably 100% by weight or less. The gypsum composition may contain gypsum, water, and commonly used additives other than the dispersants of the present invention.

The gypsum composition is used for building materials such as gypsum board and gypsum plaster, civil engineering materials such as tunnel reinforcement and ground improvement, ceramic mold materials, dental model materials, gypsum casting mold materials, etc. after being cured by heating and drying. it can.

[2-2-3. Other additives]
When the dispersant of the present invention is used as a dispersant for a hydraulic composition, it may contain the above-mentioned granular composition, and further contains an active ingredient of another cement dispersant and an active ingredient of another concrete additive. You may be. It can also be used in combination with other cement dispersants and other concrete additives. In the present specification, these are collectively referred to as "other additives".

As the active ingredient of other cement dispersants and the active ingredient of other concrete additives, for example, those listed below can be used. The active ingredients of other cement dispersants and the active ingredients of other concrete additives may be used alone or in combination of two or more.

Lignin sulfonate; polyol derivative; naphthalene sulfonic acid formalin condensate; melamine sulfonic acid formalin condensate; polystyrene sulfonate; aminoaryl sulfonic acid-phenol-formaldehyde condensate and other amino sulfonic acid compounds (for example, JP-A-1). -11341A);

A component (a) which is at least one of a copolymer of a polyalkylene glycol mono (meth) acrylic acid ester compound and a (meth) acrylic acid compound and a salt thereof, and a polyalkylene glycol mono (meth) allyl ether system. At least one of the components (b) selected from the group consisting of a copolymer of a compound and maleic anhydride, a hydrolyzate thereof, and a salt thereof, and a polyalkylene glycol mono (meth) allyl ether-based compound. A composition comprising a copolymer of a polyalkylene glycol-based compound with a maleic anhydride and a component (c) which is at least one of salts thereof (for example, JP-A-7-267705);

Component A, which is a component composed of a copolymer of (meth) acrylic acid polyalkylene glycol ester and (meth) acrylic acid (salt), component B, which is a component composed of a specific polyethylene glycol polypropylene glycol-based compound, and component B. A composition composed of a component C, which is a component composed of a specific surfactant (see, for example, Japanese Patent No. 2508113);
Consists of polyethylene (propylene) glycol ester of (meth) acrylic acid or polyethylene (propylene) glycol mono (meth) allyl ether, (meth) allyl sulfonic acid (salt), and (meth) acrylic acid (salt). A vinyl copolymer containing a unit (for example, Japanese Patent Application Laid-Open No. 62-216950);
A water-soluble vinyl copolymer obtained by polymerizing a polyethylene (propylene) glycol ester of (meth) acrylic acid, a (meth) allylsulfonic acid (salt), and a (meth) acrylic acid (salt) in an aqueous solution (for example, JP-A-Pla. 1-2267757 (see);
A combination obtained from polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) allylsulfonic acid (salt) or p- (meth) allyloxybenzenesulfonic acid (salt), and (meth) acrylic acid (salt). Polymer (see, for example, Japanese Patent Publication No. 5-36377);

A copolymer having a monomer unit formed from each of polyethylene glycol mono (meth) allyl ether and maleic acid (salt) (see, for example, JP-A-4-149056);
Constituent unit derived from polyethylene glycol ester of (meth) acrylic acid, structural unit derived from (meth) allylsulfonic acid (salt), structural unit derived from (meth) acrylic acid (salt), alkanediol mono (meth) A graft composed of a structural unit containing a polymer block derived from acrylate or polyalkylene glycol mono (meth) acrylate and obtained by radical polymerization of α, β-unsaturated monomer having an amide group in the molecule. Polymer (see, for example, Japanese Patent Application Laid-Open No. 5-170501);

Polyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) acrylate, (meth) acrylic acid alkyl ester, (meth) acrylic acid (salt), and (meth) allyl sulfonic acid (salt) or p- (meth) A water-soluble vinyl copolymer obtained by copolymerizing an allyloxybenzene sulfonic acid (salt) with an aqueous radical (see, for example, JP-A-6-191918);
Polyethylene glycol monoallyl ether, maleic acid-based monomer, and a copolymer obtained by using a monomer copolymerizable with these monomers (see, for example, Japanese Patent Publication No. 58-38380);
Polyalkylene glycol mono (meth) acrylic acid ester-based monomers, (meth) acrylic acid-based monomers, and copolymers obtained by using monomers copolymerizable with these monomers are alkaline. Copolymer obtained by neutralizing with a substance (see, for example, Japanese Patent Publication No. 59-18338);

A polymer obtained by using a polyalkylene glycol (meth) acrylic acid ester having a sulfo group and a monomer copolymerizable therewith, or a polymer obtained by neutralizing this with an alkaline substance (for example,). , Japanese Patent Application Laid-Open No. 62-119147);
An esterification reaction product of a copolymer of an alkoxypolyalkylene glycol monoallyl ether and maleic anhydride and a polyalkylene oxide derivative having an alkenyl group at the terminal (see, for example, JP-A-6-271347);
An esterification reaction product of a copolymer of an alkoxypolyalkylene glycol monoallyl ether and maleic anhydride and a polyalkylene oxide derivative having a hydroxy group at the terminal (see, for example, JP-A-6-298555);
An alkenyl ether-based monomer obtained by adding ethylene oxide or the like to a specific unsaturated alcohol such as 3-methyl-3-butene-1-ol, an unsaturated carboxylic acid-based monomer, and a copolymerizable with these monomers. Polycarboxylic acid (salt) such as a copolymer composed of a above-mentioned monomer or a salt thereof (see, for example, Japanese Patent Application Laid-Open No. 62-68806).

Other cement dispersants and other concrete additives include, for example, water-soluble polymers, polymer emulsions, air entrainers, cement wetting agents, swelling agents, waterproofing agents, retarders, thickeners, flocculants, etc. Examples thereof include dry shrinkage reducing agents, strength enhancing agents, effect promoters, defoaming agents, AE agents, separation reducing agents, self-leveling agents, rust preventives, colorants, antifungal agents and other surfactants. These may be used alone or in combination of two or more.

Examples of the water-soluble polymer include the following.
Polyacrylic acid or a salt thereof (for example, sodium salt), polymethacrylic acid or a salt thereof (for example, sodium salt), polymaleic acid or a salt thereof (for example, sodium salt), an acrylic acid / maleic acid copolymer or a salt thereof (for example, sodium salt). For example, an unsaturated carboxylic acid polymer such as sodium salt);
Nonionic cellulose ethers such as methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxypropyl cellulose;

A polysaccharide derivative having an alkylated or hydroxyalkylated derivative of a polysaccharide (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose) as a skeleton, in which some or all of the hydrogen atoms of the hydroxy group have 8 carbon atoms. A polysaccharide derivative substituted with a hydrophobic substituent having a hydrocarbon chain of ~ 40 as a partial structure and an ionic hydrophilic substituent having a sulfo group or a salt thereof as a partial structure;
Polysaccharides produced by microbial fermentation such as yeast glucan, xanthan gum, β-1,3 glucan (either linear or branched, for example, curdlan, paramylon, pakiman, scleroglucan, laminarin). ;

Polyacrylamide; polyvinyl alcohol; starch; starch phosphate ester;
Sodium alginate; gelatin; copolymer of acrylic acid having an amino group in the molecule and its quaternary compound.

Examples of the polymer emulsion include copolymers of various vinyl monomers such as alkyl (meth) acrylate.

Examples of the curing retarder other than the oxycarboxylic acid-based compound include the following.
Monosaccharides (eg glucose, fructose, galactose, saccharose, xylose, apiose, ribose, isomerized sugars), disaccharides, trisaccharides, oligosaccharides (eg dextrin), polysaccharides (eg dextran), at least one of these Sugars such as sugar compositions containing syrup (eg, sugar honey); sugar alcohols such as sorbitol; magnesium silicate; phosphoric acid and its salts or borate esters; aminocarboxylic acid and its salts; alkali-soluble proteins; humic acid Tannic acid; phenol; polyhydric alcohol such as glycerin; phosphonic acid, aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) , These alkali metal salts, phosphonic acids such as alkaline earth metal salts, and derivatives thereof.

Examples of the early-strengthening agent / accelerator include the following.
Soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide, calcium iodide; chlorides such as iron chloride and magnesium chloride; sulfates; potassium hydroxide; sodium hydroxide; carbonates; thiosulfate Garates such as formic acid and calcium formate; alkanolamine; alumina cement; calcium aluminate silicate and the like.

Examples of the defoaming agent other than the oxyalkylene type include the following.
Mineral oil defoamers such as kerosene and liquid paraffin; oil and fat defoamers such as animal and vegetable oils, sesame oil, castor oil and these alkylene oxide adducts; fatty acid defoamers such as oleic acid, stearic acid and these alkylene oxide adducts Foaming agent; fatty acid ester defoaming agent such as glycerin monolithinolate, alkenyl succinic acid derivative, sorbitol monolaurate, sorbitol trioleate, natural wax; alcohol-based defoaming agent such as octyl alcohol, hexadecyl alcohol, acetylene alcohol, glycols, etc. Foaming agent; Amido-based defoaming agent such as acrylate polyamine; Phosphate-based defoaming agent such as tributyl phosphate and sodium octyl phosphate; Metal soap-based defoaming agent such as aluminum stearate and calcium oleate; Dimethyl silicone oil, Silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethylpolysiloxane), silicone defoamer such as fluorosilicone oil, etc.

Examples of the AE agent include the following.
Resin soap; saturated or unsaturated fatty acids; sodium hydroxystearate; lauryl sulfate, ABS (alkylbenzene sulfonic acid), LAS (linear alkylbenzene sulfonic acid), alkane sulfonate, polyoxyethylene alkyl (phenyl) ether, polyoxyethylene alkyl ( Phenyl) ether sulfate esters and salts thereof; polyoxyethylene alkyl (phenyl) ether phosphate esters or salts thereof; protein materials; alkenyl sulfosuccinic acid; α-olefin sulfonate and the like.

Examples of other surfactants include the following.
An aliphatic monovalent alcohol having 6 to 30 carbon atoms in the molecule such as octadecyl alcohol and stearyl alcohol; an alicyclic monovalent alcohol having 6 to 30 carbon atoms in the molecule such as abiethyl alcohol; Monovalent mercaptan having 6 to 30 carbon atoms in a molecule such as dodecyl mercaptan; alkylphenol having 6 to 30 carbon atoms in a molecule such as nonylphenol; 6 to 30 carbons in a molecule such as dodecylamine Amines with atoms; Polyalkylene oxide derivatives in which 10 mol or more of alkylene oxides such as ethylene oxide and propylene oxide are added to carboxylic acids having 6 to 30 carbon atoms in molecules such as lauric acid and stearic acid; alkyl Alkyldiphenyl ether sulfonates in which two phenyl groups having a sulfo group are ether-bonded, which may have a group or an alkoxy group as a substituent;

Various anionic surfactants other than the above; various cationic surfactants such as alkylamine acetate and alkyltrimethylammonium chloride; various nonionic surfactants; and various amphoteric surfactants.

Examples of the waterproofing agent include the following.
Fatty acids (salts), fatty acid esters, fats and oils, silicones, paraffins, asphalt, waxes, etc.

Examples of the rust preventive include nitrite, phosphate and zinc oxide.

Examples of the crack reducing agent include polyoxyalkyl ether.

Examples of the expansion material include an ettringite type and a coal type.

When the dispersant of the present invention is used in combination with another additive, the mixing ratio of the dispersant of the present invention and the other additive (that is, the dispersant of the present invention / other additive: weight ratio in terms of solid content) ) Is preferably 1 to 99/99 to 1, more preferably 5 to 95/95 to 5, still more preferably 10 to 90/90 to 10, and even more preferably 20 to 80/80. ~ 20.

[2-2-4. Oxycarboxylic acid compounds]
The dispersant of the present invention may be used in combination with an oxycarboxylic acid compound in addition to the above-mentioned other cement dispersants and other concrete additives. As a result, even in a high temperature environment, higher dispersion holding performance can be exhibited.

As the oxycarboxylic acid-based compound, an oxycarboxylic acid having 4 to 10 carbon atoms or a salt thereof is preferable. More specifically, examples thereof include gluconic acid, glucoheptonic acid, arabonic acid, malic acid, citric acid, and inorganic salts or organic salts such as sodium, potassium, calcium, magnesium, ammonium, and triethanolamine. These oxycarboxylic acid compounds may be used alone or in combination of two or more.

Among the above oxycarboxylic acid compounds, gluconic acid or a salt thereof is preferable. In particular, in the case of poorly mixed concrete, a lignin sulfonate-based dispersant should be used as the sulfonic acid-based dispersant having a sulfo group in the molecule, and gluconic acid or a salt thereof should be used as the oxycarboxylic acid-based compound. Is preferable.

When the dispersant of the present invention and the oxycarboxylic acid compound are used in combination, the blending ratio of the dispersant of the present invention and the oxycarboxylic acid compound (that is, the dispersant / oxycarboxylic acid compound of the present invention in terms of solid content: The weight ratio) is preferably 1 to 99/99 to 1, more preferably 5 to 95/95 to 5, still more preferably 10 to 90/90 to 10, and even more preferably 20 to 80. / 80 to 20.

When the three components of the dispersant of the present invention, other additives and the oxycarboxylic acid compound are used in combination, the blending ratio of the dispersant of the present invention, the other additive and the oxycarboxylic acid compound (that is, by solid content conversion) The dispersant / other additive / oxycarboxylic acid compound: weight ratio) of the present invention is preferably 1 to 98/1 to 98/1 to 98, more preferably 5 to 90/5 to 90/5. It is ~ 90, more preferably 10-90 / 5-85 / 5-85, and even more preferably 20-80 / 10-70 / 10-70.

Hereinafter, the present invention will be described in detail with reference to Examples. The following examples are for the purpose of preferably explaining the present invention, and do not limit the present invention. Unless otherwise specified, the method for measuring the physical property value or the like is the measurement method described above. In the examples, unless otherwise specified, "%" indicates% by weight, and "parts" indicates parts by weight.

[Pyrolysis point (° C.)]: Measured by the following procedure using a thermogravimetric differential thermal analyzer (TG-DTA) (trade name "STA7200", manufactured by SII).
A granular composition having a solid content of 10 g or a target sample was dried and solidified at 105 ° C. About 10 mg of the solidified sample was heated from 50 ° C. to 600 ° C. at a heating rate of 10 ° C./min under a nitrogen atmosphere (nitrogen gas introduction amount 100 mL / min). The temperature at which the weight loss rate of the sample was maximum was defined as the thermal decomposition point. The measurement was performed three times for each sample, and the average value was used.
When the target sample is a polycarboxylic acid, it is dried and solidified for one day at -20 ° C by a freeze dryer (trade name "FDU-1200", manufactured by Tokyo Rika Kikai Co., Ltd.), or a blower dryer (trade name "FDU-1200"). Blower constant temperature incubator DKM600 ”, manufactured by Yamato Kagaku Co., Ltd.) was used for one-day drying and solidification at 105 ° C. Other than that, it was dried at 180 ° C. using a spray dryer (trade name "TR120", manufactured by Pris).

[Thermogravimetric reduction rate (%)]: Measured by the following procedure using a thermogravimetric differential thermal analyzer (TG-DTA) (trade name "STA7200", manufactured by SII).
A granular composition having a solid content of 10 g or a target sample was dried and solidified at 105 ° C. About 10 mg of the solidified sample was heated from 50 ° C. to 600 ° C. at a heating rate of 10 ° C./min under a nitrogen atmosphere (nitrogen gas introduction amount 100 mL / min). The rate of weight loss of the sample up to 600 ° C. was defined as the thermogravimetric weight loss rate. The measurement was performed three times for each sample, and the average value was used.
When the target sample is a polycarboxylic acid, it is dried and solidified for one day at -20 ° C by a freeze dryer (trade name "FDU-1200", manufactured by Tokyo Rika Kikai Co., Ltd.), or a blower dryer (trade name "FDU-1200"). Blower constant temperature incubator DKM600 ”, manufactured by Yamato Kagaku Co., Ltd.) was used for one-day drying and solidification at 105 ° C. Other than that, it was dried at 180 ° C. using a spray dryer (trade name "TR120", manufactured by Pris).

[Weight average molecular weight]: Measured by gel permeation chromatography (GPC) in terms of polyethylene glycol. The details of the measurement conditions of GPC are described below.
Measuring device; Column used by Tosoh; Shodex Volume OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ
Eluent; 0.05 mM sodium nitrate / acetonitrile 8/2 (v / v)
Standard substance: Polyethylene glycol (manufactured by Tosoh or GL Science)
Detector; differential refractometer (manufactured by Tosoh)

[Example 1: Production of granular composition (1)]
In a glass reaction vessel equipped with a thermometer, agitator, reflux device, and dropping device, 229 g of water, 92 g of poly (ethylene oxide) monophenyl ether (EO addition molar number: 50), Sunflow RH (lignin sulfonate, Japan). 60 g (manufactured by Paper Manufacturing Co., Ltd.), 13 g of 37% aqueous formaldehyde solution, 55 g of 72% aqueous sulfuric acid solution, and 0.05 g of antifoaming agent Pronal 753 (manufactured by Toho Kagaku Co., Ltd.) were charged, and the temperature of the reaction vessel was raised to 105 ° C. under stirring. The reaction was completed at a liquid temperature of 105 ° C. for 14 hours. After completion of the reaction, the temperature of the reaction product was lowered to 90 ° C., 93 g of a 250 g / L aqueous calcium hydroxide solution and 24 g of a 31% aqueous sodium hydroxide solution were added to the reaction vessel, and the mixture was further stirred for 1 hour. By filtering these mixtures to remove the gypsum produced by neutralization, a lignin derivative containing a copolymer having a weight average molecular weight of 41,300 was obtained. The reaction weight ratio of the lignin sulfonic acid compound [L] and the water-soluble compound [M] was [L] / [M] = 39/61, and the reaction rate of the water-soluble compound was 95%. This lignin derivative was dried at 180 ° C. using a spray dryer (trade name “TR120”, manufactured by Pris) to obtain the granular composition (1) of the present invention as a solid substance.
The thermal decomposition point of the granular composition (1) was 395 ° C., and the thermogravimetric reduction rate was 68%.

[Example 2: Production of granular composition (2)]
In a glass reaction vessel equipped with a thermometer, agitator, reflux device, and dropping device, 275 g of water, 69 g of poly (ethylene oxide) monophenyl ether (number of moles added: 50), Sunflow RH (lignin sulfonate, Japan). 150 g (manufactured by Paper Manufacturing Co., Ltd.), 12 g of 37% aqueous formaldehyde solution, 40 g of 72% aqueous sulfuric acid solution, and 0.05 g of antifoaming agent Pronal 753 (manufactured by Toho Kagaku Co., Ltd.) were charged, and the temperature of the reaction vessel was raised to 105 ° C. under stirring. The reaction was completed at a liquid temperature of 105 ° C. for 10 hours. After cooling the reaction solution, 85 g of a 250 g / L calcium hydroxide aqueous solution was added to the reaction vessel. By filtering these mixtures to remove the gypsum produced by neutralization, a lignin derivative containing a copolymer having a weight average molecular weight of 22,800 was obtained. The reaction weight ratio of the lignin sulfonic acid compound [L] and the water-soluble compound [M] was [L] / [M] = 68/32, and the reaction rate of the water-soluble compound was 89%. This lignin derivative was dried at 180 ° C. using a spray dryer (trade name “TR120”, manufactured by Pris) to obtain the granular composition (2) of the present invention as a solid substance.
The thermal decomposition point of the granular composition (2) was 390 ° C., and the thermogravimetric reduction rate was 68%.

[Example 3: Production of granular composition (3)]
Ligno sulfonic acid (trade name "Sunflow RH", manufactured by Nippon Paper Industries Co., Ltd.) having a tangible appearance of 175 g and a solid content of 70 g, and a polycarboxylic acid-based dispersant having a tangible appearance of 120 g and a solid content of 30 g (trade name "SF-500R"). It was mixed with Floric (manufactured by Floric) and dried at 180 ° C. using a spray dryer (trade name “TR120”, manufactured by Pris) to obtain the granular composition (3) of the present invention as a solid.
The weight ratio of the lignin sulfonic acid compound [L] to the water-soluble compound [M] was [L] / [M] = 70/30.
The thermal decomposition point of the granular composition (3) was 236 ° C., and the thermogravimetric reduction rate was 65%.

[Comparative Example 1: Production of Control Sample (1)]
Naphthalene sulfonic acid (trade name "Sunflow PS", manufactured by Nippon Paper Industries Co., Ltd.) was dried at 180 ° C. using a spray dryer (trade name "TR120", manufactured by Pris) to obtain a control sample (1) as a solid substance. It was.
The pyrolysis point of the control sample (1) was 495 ° C., and the thermogravimetric reduction rate was 20%.

[Comparative Example 2: Production of Control Sample (2)]
733 parts of water was charged in a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device, the reaction vessel was replaced with nitrogen under stirring, and the temperature was raised to 100 ° C. under a nitrogen atmosphere. After that, 21 parts of methacrylic acid, 30 parts of acrylic acid, 92 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added 25), 70 parts of water were mixed in a monomer aqueous solution, and 3 parts of ammonium persulfate and 87 parts of water were added. The mixed solution was continuously added dropwise to the reaction vessel kept at 50 ° C. for 2 hours each. Further, the aqueous solution of the polycarboxylic acid-based dispersant obtained by reacting for 1 hour while maintaining the temperature at 50 ° C. was adjusted to pH 7 with a 31% NaOH aqueous solution. The polycarboxylic acid-based dispersant in the liquid had a weight average molecular weight of 18,300 (Mw / Mn1.6). This polycarboxylic acid-based dispersant was dried at −20 ° C. using a freeze-dryer (trade name “FDU-1200”, manufactured by Tokyo Rika Kikai Co., Ltd.) to obtain a control sample (2) as a solid substance. The pyrolysis point of the control sample (2) was 405 ° C., and the thermogravimetric reduction rate was 85%.

[Comparative Example 3: Production of Control Sample (3)]
A polycarboxylic acid-based dispersant (trade name "SF-500R", manufactured by Floric Co., Ltd.) was dried at 105 ° C. for 1 day using a dryer (trade name "Blower constant temperature incubator DKM600", manufactured by Yamato Scientific Co., Ltd.). A control sample (3) was obtained as a solid.
The pyrolysis point of the control sample (3) was 335 ° C., and the thermogravimetric reduction rate was 88%.

[Comparative Example 4: Production of Control Sample (4)]
Ligno sulfonic acid (trade name "Sunflow RH", manufactured by Nippon Paper Industries Co., Ltd.) is dried at 180 ° C. using a spray dryer (trade name "TR120", manufactured by Pris) to obtain a control sample (4) as a solid substance. It was.
The pyrolysis point of the control sample (4) was 310 ° C., and the thermogravimetric reduction rate was 47%.

<Concrete test>
Concrete (cement composition, hydraulic composition) to which the granular compositions or control samples of Examples 1 to 3 and Comparative Examples 1 to 4 were added was prepared by the following procedure, and the obtained concrete was subjected to a slump test. ..

<Concrete test procedure and evaluation method: Examples 1 to 3, Comparative Examples 1 to 4>
In a high temperature environment (40 ° C.) assuming summer, the coarse aggregate, fine aggregate, and cement blended as shown in Table 1 were added and kneaded for 10 seconds by mechanical kneading with a forced biaxial mixer. Next, water and the granular composition or control sample (initial addition) shown in Table 2 were added in the amounts shown in Table 2, kneaded for 90 seconds, and then some concrete was discharged to perform a fresh concrete test (fresh concrete test). The slump test JIS A 1101 (measured by measuring the spread of fresh concrete as a flow value) was performed to evaluate the initial concrete. Further, the prepared concrete was allowed to stand in a high temperature environment (40 ° C.) for a predetermined time, and then ( The fresh concrete test was carried out after 15 minutes, 30 minutes, or 45 minutes). The results are shown in Table 2.

Details of the symbols in Table 1 are shown below.
C: Equal weight mixture of the following three types of cement Ordinary Portland cement (manufactured by Ube-Mitsubishi Cement Co., Ltd., specific gravity 3.16)
Ordinary Portland cement (manufactured by Taiheiyo Cement, specific density 3.16)
Ordinary Portland cement (made by Tokuyama, specific density 3.16)
W: Tap water S1: Lime crushed sand from Tsukumi, Oita Prefecture (fine aggregate, specific density 2.66)
S2: Crushed stone crushed sand from Shunan, Yamaguchi Prefecture (fine aggregate, specific density 2.66)
G1, G2: Crushed stone from Iwakoku, Yamaguchi Prefecture (coarse aggregate, specific density 2.73 (G1), 2.66 (G2))

In Table 2, the numerical value of the addition amount is the solid content weight (%) of each granular composition or control sample with respect to the cement weight.

The following can be said from Table 2. The granular compositions (1) to (3) have a thermogravimetric reduction rate of 65% or 68%, have good heat resistance, and have excellent dispersibility in a high temperature environment of 40 ° C. assuming summer. (See Examples 1 to 3). In particular, the granular composition further containing the lignin derivative has a thermal decomposition point of 395 ° C. and 390 ° C., and can improve heat resistance without causing a decrease in dispersibility due to resinification (see Examples 1 and 2). ..
On the other hand, in the control samples (1) to (4) in which the known dispersant is solidified, the thermogravimetric reduction rate is as low as 20% or 47%, and does it cause a decrease in dispersibility due to impurities unavoidably mixed? (See Comparative Examples 1 and 4), 85% or 88%, which was excessively high and inferior in heat resistance (see Comparative Examples 2 and 3). Further, the thermal decomposition point is also low at 310 ° C. or 335 ° C., which is inferior in heat resistance (see Comparative Examples 3 and 4), or high at 405 ° C., 495 ° C., which is inferior in the decrease in dispersibility due to resinification. (See Comparative Examples 1 and 2).

Claims (8)

With lignin sulfonic acid compounds
It contains an aromatic water-soluble compound having a polyalkylene oxide chain having an average number of moles of alkylene oxide added of 35 to 150.
The thermogravimetric reduction rate, which is the rate of weight loss up to 600 ° C., measured when the temperature is raised from 50 ° C. to 600 ° C. at a heating rate of 10 ° C./min by a thermogravimetric differential thermal analyzer, is 50 to 80. % And a granular composition having a thermal decomposition point of 350 ° C. or higher and lower than 400 ° C., which is the temperature at which the weight loss rate of the sample is maximum. The granular composition according to claim 1, further comprising a lignin derivative which is a reaction product of a lignin sulfonic acid-based compound and a water-soluble compound. The granular composition according to claim 2 , wherein the lignin derivative has an anionic functional group. In the lignin derivative, the reaction weight ratio ([L] / [M]) of the lignin sulfonic acid-based compound [L] and the aromatic water-soluble compound [M] is 1 to 99/99 to 1. The granular composition according to claim 2 or 3. The aromatic water-soluble compound is selected from the group consisting of an aromatic water-soluble compound having a polyalkylene oxide chain, an aromatic water-soluble compound having a carboxyl group, and an aromatic water-soluble compound having a sulfo group. The granular composition according to any one of claims 1 to 4 , which comprises 1 or more. Any of claims 2 to 5 containing a lignin derivative in which the reaction rate of the aromatic water-soluble compound, which is the ratio of the amount after the reaction to the amount before the reaction with the lignin sulfonic acid compound, is 50% or more. The granular composition according to item 1. A dispersant containing the granular composition according to any one of claims 1 to 6. The dispersant according to claim 7 , which is a muddy water dispersant for oil field excavation or a dispersant for a hydraulic composition.