JP2020026459A - Granular composition and dispersant - Google Patents

Abstract

To provide a solid matter of a lignin-containing composition exhibiting high dispersibility and excellent in heat resistance.SOLUTION: There is provided a granular composition containing a lignin sulphonic acid-containing compound and a water-soluble compound, and having heat weight loss rate measured by a thermogravimetry differential thermal analysis device of 50 to 80%.SELECTED DRAWING: None

Description

  The present invention relates to particulate compositions and dispersants.

  Lignin is a natural polymer component present in trees, and is occurring on a large scale and commercially in the paper industry using wood as a raw material. For example, kraft pulp waste liquor yields kraft lignin, and sulfite pulp waste liquor yields lignin sulfonic acid. Kraft lignin and ligninsulfonic acid, or their processed products, are used as dispersants as dyes, hydraulic compositions (eg, cement, gypsum), inorganic and organic pigments, coal-water slurries, pesticides, ceramics, oilfield drilling mud, etc. 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 use for oil field drilling (for example, see Patent Documents 1 and 2). It has been shown that these lignin derivatives have low viscosity values after high-temperature histories and are excellent in thermal properties.

JP 2011-240224 A JP 2011-240223 A

  Lignin sulfonic acid is generally known to have poor heat resistance. Therefore, when it is used for excavation or cement dispersion at high temperatures such as in summer, heat resistance at higher temperatures is required, and there is room for improvement.

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

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

  ADVANTAGE OF THE INVENTION According to this invention, the solid of the lignin containing composition which shows high dispersibility and is excellent in heat resistance can be provided.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments. In this specification, the notation “AA to BB” means AA or more and BB or less. Further, the thermogravimetric differential thermal analyzer is also described as “TG-DTA”.

[1. Granular composition]
The granular composition of the present invention contains a ligninsulfonic 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 by TG-DTA of 350 ° C or more and less than 400 ° C.

[1-1. Physical properties]
In the granular composition of the present invention, the lower limit of the thermal weight loss rate measured by TG-DTA is 50% or more, preferably 55% or more, and more preferably 60% or more. When the content is 50% or more, the ash content is low, the inhibitory effect of the inevitable impurities other than the lignin derivative on the dispersant is suppressed, and high dispersibility can be secured. The upper limit is 80% or less, preferably 75% or less, and more preferably 70% or less. When it is at most 80%, heat resistance can be ensured. Therefore, the thermal weight loss rate measured by TG-DTA is 50 to 80%, preferably 55 to 75%, more preferably 60 to 70%.

  The lower limit of the thermal decomposition point measured by TG-DTA of the granular composition of the present invention is preferably 350 ° C or higher, more preferably 360 ° C or higher, and further preferably 370 ° C or higher. When the temperature is 350 ° C. or higher, heat resistance can be ensured. Moreover, the upper limit is less than 400 degreeC, Preferably it is 398 degreeC or less, More preferably, it is 396 degreeC or less. When the temperature is lower than 400 ° C., resinification of the granular composition can be suppressed, and the granular composition can function as a dispersant or a binder. Therefore, the thermal decomposition point measured by TG-DTA is preferably 350 ° C. or more and less than 400 ° C., more preferably 360-398 ° C., and even more preferably 370-396 ° C.

In addition, the thermal decomposition point and the thermogravimetric reduction rate measured by TG-DTA are values measured using a thermogravimetric differential scanning calorimeter (TG-DTA) (trade name “STA7200”, manufactured by SII). .
More specifically, it is a value measured by the following procedure. Dry and solidify 10 g of the granular composition. The method of drying and solidifying is: 1) a method of drying and solidifying at 105 ° C. for 1 day by a dryer (trade name “Blower constant temperature thermostat DKM600”, manufactured by Yamato Scientific Co., Ltd.), 2) a freeze dryer (trade name “FDU- 1200 "(manufactured by Tokyo Rika Kikai Co., Ltd.) and a method of drying and solidifying at -20 ° C. for 1 day. 3) A method of drying and solidifying 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 rate of 10 ° C./min in a nitrogen atmosphere. The temperature at which the weight reduction rate of the sample is maximum is defined as the thermal decomposition point, and the weight reduction rate up to 600 ° C. is defined as the thermal weight reduction rate. The measurement is performed three times for one sample, and the average value is obtained.

  The thermal decomposition point and the thermal weight loss rate measured by TG-DTA can be adjusted by appropriately adjusting the types and amounts of the ligninsulfonic acid-based compound, the water-soluble compound, and the lignin derivative. In particular, when a lignin derivative is contained, it can be adjusted by appropriately designing the reaction conditions of the lignin derivative. 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 making appropriate changes.

[1-2. Lignin sulfonic acid compound]
The lignin sulfonic acid compound is a compound having a skeleton in which a carbon at the α-position of the side chain of the hydroxyphenylpropane structure of lignin is cleaved to introduce a sulfo group (sulfonic acid group). Formula (1) shows the structure of the skeleton.

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

  The ligninsulfonic 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, a calcium salt, a magnesium salt, a sodium salt, a calcium / sodium mixed salt and the like are preferable.

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

  Lignin sulfonic acid-based compounds (modified lignin sulfonic acid-based compounds) are abundant in commercially available products, and such commercially available products may be used in the present invention. Examples of commercially available products include Vanirex HW (manufactured by Nippon Paper), Sun Extract M (manufactured by Nippon Paper), Pearl Rex NP (manufactured by Nippon Paper), and Sunflow RH (manufactured by Nippon Paper).

  The ligninsulfonic acid-based compound usually has at least one functional group site capable of reacting with a water-soluble compound. Examples of such a site 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. Above all, 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 liquor, that is, a compound capable of reacting with the main component of the sulfite pulp waste liquor. The functional group contained in the ligninsulfonic acid-based compound (eg, phenolic hydroxyl group, alcoholic hydroxyl group, carboxyl group) And a thiol group) are preferable. The form of the chemical reaction is not particularly limited, and includes a radical reaction, an ionic bond, a coordination bond, a condensation reaction, a reaction involving hydrolysis, a reaction involving dehydration, a reaction involving oxidation, a reaction involving reduction, and a reaction involving neutralization. Is exemplified.

  The aromatic water-soluble compound preferably has at least one polar group. This makes it easier to control the physical properties of the granular composition, and improves the reactivity when reacting with the ligninsulfonic acid-based compound. 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 phosphate group, an amino group, and an epoxy group. The aromatic water-soluble compounds may be used alone or in a 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] with [B] and / or [C].

([A] Aromatic water-soluble compound having 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 an ethylene oxide unit, a propylene oxide unit, and a butylene oxide unit. Especially, an ethylene oxide unit or a propylene oxide unit is preferable.
The average number of added moles of the alkylene oxide unit 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. Thereby, a 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 still more preferably 35 to 150. Note that the above average number of moles added is a guide. Regardless of whether or not the above range is satisfied, [A] has an alkylene oxide unit which is not repeatedly added (monoalkylene oxide group). You may.

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

  [A] includes, for example, oxyalkylene group adducts to aromatic compounds such as phenol, cresol, nonylphenol, naphthol, methylnaphthol, butylnaphthol, bisphenol A and bisphenol S. More specifically, examples thereof include polyalkylene oxide alkyl phenyl ethers, polyalkylene oxide phenyl ethers, polyalkylene oxide alkyl naphthyl ethers, and polyalkylene oxide naphthyl ethers. Among these, a benzene ring derivative is preferable since at least co-condensability can be improved, and at least one of polyalkylene oxide alkyl phenyl ethers and polyalkylene oxide phenyl ethers is more preferable. Oxyalkylene group adducts to phenol) (for example, poly (ethylene oxide) monophenyl ether, poly (propylene oxide) monophenyl ether, and the preferred range of the average addition mole number of ethylene oxide units and propylene oxide units are as described above). preferable. [A] may be one kind or a combination of two or more kinds.

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

([C] Aromatic water-soluble compound having a sulfo group)
[C] includes, for example, alkylnaphthalenesulfonic acid, alkylphenolsulfonic acid, anilinesulfonic acid, and alkylbenzenesulfonic acid. More specifically, mention may be made of naphthalenesulfonic acid, methylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, phenolsulfonic acid, cresolsulfonic acid, anilinesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, isomers and condensates thereof. Examples of the condensate include a naphthalenesulfonic acid formaldehyde condensate. Since the reactivity is good, a phenol derivative having a sulfo group and anilinesulfonic acid are preferred, and phenolsulfonic acid and anilinesulfonic acid are more preferred. [C] may be one kind or a combination of two or more kinds.

([D] Other aromatic water-soluble compounds)
[D] includes aromatic water-soluble compounds other than [A] to [C], for example, (alkyl) phenols such as phenol and cresol. [D] may be one kind or a combination of two or more kinds.

(Known (co) polymer)
Known (co) polymers include, for example, polymers derived from (poly) alkylene glycol alkenyl ether-based monomers; water-soluble polyalkylene glycols whose both terminal groups are hydrogen atoms; polyoxyalkylene structural units; Copolymers having at least two structural units selected from the group consisting of carboxylic acid structural units and polyester structural units (for example, WO2018 / 56124).

[1-4. [E] Other aromatic compounds]
The granular composition of the present invention may contain [E] another aromatic compound in addition to the ligninsulfonic acid compound and the water-soluble compound. [E] includes, for example, simple aromatic hydrocarbon compounds such as benzene and naphthalene. [E] may be one kind or a combination of two or more kinds.

  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 the other aromatic compound ([E]) ([ L]: [M]: [E]) is preferably from 30 to 90:10 to 70: 0 to 5, more preferably from 40 to 85:15 to 60: 0 to 3, and from 50 to 80:20 to 50: 0 to 2 is more preferred.

[1-5. Lignin derivative]
It is preferable that the granular composition of the present invention further contains a lignin derivative that is a reaction product of a ligninsulfonic acid-based compound and a water-soluble compound. The lignin derivative is usually a polymer containing a constituent unit derived from a ligninsulfonic acid-based compound and a constituent unit derived from a water-soluble compound. In addition, the lignin derivative may include a constituent unit derived from another aromatic compound.
It is difficult to uniformly specify the chemical structure of the lignin derivative using a general formula or the like. The reason is that lignin, which is the skeleton of the lignin sulfonic acid 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 the molecule. Thereby, the dispersibility of the dispersant can be further improved.

  The anionic functional group means a functional group that takes an anionic form in water, and includes, for example, 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 included in a structural unit derived from a water-soluble compound in the lignin derivative, or may be included in a part of a structural unit derived from a lignin sulfonic acid-based compound, or both. May be included.
The anionic functional group in the lignin derivative can be quantitatively and qualitatively observed by NMR, IR or other instrumental analysis.

  The lignin derivative preferably has a polyalkylene oxide chain in the 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 an ethylene oxide unit, a propylene oxide unit, and a butylene oxide unit. Especially, an ethylene oxide unit or a propylene oxide unit is preferable.

  The average number of added moles of the alkylene oxide unit 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. Thereby, a 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 still more preferably 35 to 150.

The polyalkylene oxide chain may be included in a part of the structural unit derived from the lignin sulfonic acid-based compound among the lignin derivatives, or may be included in the structural unit derived from the water-soluble compound, or both. May be included, and preferably included in the latter.
The polyalkylene oxide chain in the lignin derivative can be quantitatively and qualitatively observed by NMR, IR or other instrumental analysis.

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

  As the ligninsulfonic acid-based compound used as a raw material in the preparation of the lignin derivative, a powder processed product that has undergone a treatment such as a powder drying treatment may be used. Handling is facilitated by the powder.

From the viewpoint of reactivity, the water-soluble compound is preferably an aromatic water-soluble compound having at least one aromatic skeleton, more preferably an aromatic water-soluble compound having at least one polar group. 1 or more selected from the group consisting of [C] to [C] is more preferable, and only [A] alone or a combination of [A] with [B] and / or [C] is still more preferable.
Hereinafter, an example in which an aromatic water-soluble compound is used as the water-soluble compound will be described.

  As a method of chemically bonding a ligninsulfonic acid compound and an aromatic water-soluble compound, a method of condensing an aromatic water-soluble compound with a ligninsulfonic acid compound (for example, formaldehyde condensation), a radical reaction, an ionization method, Binding is exemplified. More specifically, a method in which formaldehyde is added to a ligninsulfonic acid-based compound and bonded to an aromatic water-soluble compound; hydrogen radicals are extracted and generated by, for example, allowing a radical initiator to act on the ligninsulfonic acid-based compound. A method of causing a radical reaction between a radical and at least one aromatic water-soluble compound is exemplified.

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

When reacting an aromatic water-soluble compound with a ligninsulfonic acid-based compound, any of a reaction reaction and a bulk reaction can be employed. 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. And ketones such as acetone and methyl ethyl ketone; and cyclic ethers such as tetrahydrofuran and dioxane. Among them, it is preferable to use at least one of water and a lower alcohol, and it is more preferable to use water. Thereby, the solubility aspect of the raw material monomer and the obtained copolymer and the step of removing the solvent can be omitted.
In addition, a solvent may be used individually by 1 type, and may use 2 or more types together (for example, water-alcohol mixed solvent).

  When preparing the lignin derivative, an antifoaming agent may be used. Thereby, 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 to allow the reaction to proceed stably. Therefore, when the reaction is performed by solution polymerization, the dissolved oxygen concentration at 25 ° C. of the solvent used is preferably 5 ppm or less, more preferably 0.01 to 4 ppm, still more preferably 0.01 to 2 ppm, and still more preferably. Can be adjusted in the range of 0.01 to 1 ppm. Adjustment of the dissolved oxygen concentration may be performed in a reaction tank, or may be performed before the reaction.

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

  In preparing 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 performed 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 performed in the acidic region as it is. When the reaction system is not acidic, the reaction may be carried out at a pH of 2 or less by adding an acid catalyst such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid or p-toluenesulfonic acid in advance. A preferred acid is sulfuric acid, but may be other than the above specific examples and is not limited.

The reaction weight ratio ([L] / [M]) of the lignin sulfonic acid compound [L] and the aromatic water-soluble compound [M] constituting the lignin derivative 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 still 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 provided 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 as (solid weight of lignin sulfonic acid compound before reaction) / (solid weight of aromatic water-soluble compound before reaction). It is measured in.

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 resulting lignin derivative can exhibit good dispersibility.
The reaction rate of the aromatic water-soluble compound can be measured as follows, and is also measured by this method in the 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, assuming that 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 compounds and other aromatic compounds) other than the lignin sulfonic acid compound used when preparing the lignin derivative is not particularly limited, but the following reaction weight ratios are preferred. [A]: [B]: [C]: ([D] + [E]) = Reaction weight ratio of 50 to 100% by weight: 0 to 50% by weight: 0 to 50% by weight: 0 to 10% by weight It is preferred that However, [A] + [B] + [C] + [D] + [E] = 100% by weight.
Here, [A] to [E] correspond to the compounds described above.

  The reaction solution after the completion of the condensation reaction is preferably subjected to a post-treatment by heat at a temperature of 60 to 120 ° C. under a pH condition of 8.0 to 13.0. The post-treatment by heat is usually performed 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 lieu of the removal of free formaldehyde by the so-called Cannizzaro reaction described above, of course, other methods for reducing excess formaldehyde known, for example, in the field of melamine-formaldehyde resin and phenol-formaldehyde resin chemistry are known. May go. Examples of such a method include addition of a formaldehyde absorbent (addition of a small amount of sodium bisulfite, addition of hydrogen peroxide).

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

For neutralization, a neutralizing agent that can neutralize a reaction product and a 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, Ba (OH) _{2 and the} like can be mentioned. As a result, calcium sulfate and barium sulfate having low solubility are formed together with free sulfuric acid, and are precipitated 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. Further, unwanted sodium sulfate may be separated off by dialysis or ultrafiltration.

  When by-products such as sodium sulfate, calcium sulfate, and their hydrates are generated in the addition and neutralization of the basic compound, the basic compound is added in a heated state after the reaction, and the heated state is reduced. It is preferable to improve the removability of the by-product by keeping the temperature. The heating is preferably performed at a temperature of 40 ° C. or higher. The holding time of the heated state is preferably 30 minutes or more.

The lignin derivative may be any reaction product obtained by the above-described reaction, and may be either a free acid or a neutralized salt thereof. Neutralized salts are preferred because the polymer can be easily stored and used. Examples of the neutralized salt of the reaction product include an alkali metal salt such as a sodium salt or a potassium salt; an alkaline earth metal salt such as a calcium salt; an ammonium salt; and a salt of an organic amine.
After completion of the reaction, the concentration of the obtained lignin derivative may be adjusted as necessary.

(Physical properties of lignin derivatives)
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 further preferably 5,000 to 100. , 000. The weight average molecular weight can be measured by gel permeation chromatography (GPC) by a known method in terms of polyethylene glycol.

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

[1-6. Optional component]
The granular composition of the present invention may contain optional components in addition to the above as long as the effects of the present invention are not impaired. Optional components include hydraulic composition dispersants (eg, cement dispersants, gypsum dispersants), oil field drilling mud dispersants, dye dispersants, chelating agents, detergents, flocculants, thickeners, coating agents, Examples include paints, adhesives, and water-absorbing resins.

[1-7. Method for producing granular composition]
The granular composition of the present invention may be produced by separately mixing (1) a ligninsulfonic acid-based compound and a water-soluble compound and then drying the mixture, and (2) a ligninsulfonic acid-based compound and a water-soluble compound. A lignin derivative, which is a reaction product with, is prepared and dried. When preparing a lignin derivative, a lignin sulfonic acid 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 and magnesium to form a polyvalent metal salt and then drying; drying by supporting an inorganic powder such as a silica-based fine powder and the like Method: a method of drying and solidifying 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); and a method of drying and solidifying with a spray dryer.

[2. Dispersant]
The dispersant of the present invention contains the above granular composition and can be used for various uses. For example, dispersants for hydraulic compositions (for example, dispersants for cement, dispersants for gypsum), mud dispersants for oilfield drilling, dispersants for dyes, chelating agents, detergents, flocculants, thickeners, coating agents , Paints, adhesives, and water-absorbing resins. The granular composition of the present invention shows high dispersibility and is excellent in heat resistance. Therefore, a slurry dispersant for oil field drilling or a dispersant for hydraulic compositions is preferred.

[2-1. Mud dispersant for oil field drilling]
The dispersant of the present invention can be used as a mud dispersant for oil field drilling. The mud for oil field drilling may be mud used as a fluid circulating in the well during oil field drilling and / or recovery work, and its composition is not particularly limited. Oilfield drilling muds are generally classified into water-based and oil-based, with water-based mud being preferred. Aqueous mud usually contains clay.
Examples of the clay include montmorillonite and bentonite. Among them, bentonite is preferred.

  The pH of the mud for oil field drilling is not particularly limited, but is preferably 9 to 13, more preferably 9.5 to 11.5, and even more preferably about 11. The temperature of the oil field drilling mud 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 muddy water for oilfield drilling 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 at most 30% by weight, more preferably at most 20% by weight.

[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 dispersion target include various hydraulic materials. Hydraulic materials are classified into cement compositions such as cement and gypsum, and other hydraulic materials, and any of them may be used. The dispersant of the present invention can constitute a hydraulic composition together with the hydraulic material and water as a hydraulic composition dispersant. The hydraulic composition may further include fine aggregate (sand or the like) or coarse aggregate (crushed stone or the like) as necessary. Examples of the hydraulic material include cement paste, mortar, concrete, and plaster.

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

Cement that can be used in the cement composition is not particularly limited, but specific examples include the following.
Portland cement (ordinary, fast strong, super fast, moderate heat, sulfate resistant and low alkali type of each); various mixed cements (blast furnace cement, silica cement, fly ash cement); white Portland cement; alumina cement; Cement (1 clinker fast setting cement, 2 clinker fast setting cement, magnesium phosphate cement); grout cement; oil well cement; low heat generating cement (low heat generating blast furnace cement, low heat generating blast furnace cement mixed with fly ash, high content of belite Cement); ultra-high-strength cement; cement-based solidifying material; eco-cement (cement manufactured using at least one of municipal solid waste incineration ash and sewage sludge incineration ash).

Components other than the above cement may be added to the cement composition. 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, siliceous, clay) , Zircon, high alumina, silicon carbide, graphite, chromium, chromium, magnesia, 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.
Unit water content is preferably 100~185kg / ^{m 3,} more preferably from 120~175kg / ^{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 from 0.15 to 0.7, and more preferably from 0.25 to 0.65.

The dispersant of the present invention may be used in a cement composition in a high water reduction area, that is, 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 unit cement amount and a small water / cement ratio, and poorly-mixed concrete with a small amount of cement (unit cement amount) (for example, about 300 kg / m ³ or less). .

In the cement composition (for example, when used for mortar or concrete using hydraulic cement), the lower limit of the amount of the dispersant of the present invention is preferably 0.1 to 0.1 wt. It is at least 01% by weight, more preferably at least 0.02% by weight, even more preferably at least 0.05% by weight. When the amount is 0.01% by weight or more, the dispersion performance can be sufficiently exhibited. The upper limit 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. When the content is 10.0% by weight or less, the effect of improving dispersibility can be economically advantageous without substantially saturating, and adverse effects on the properties of mortar and concrete, such as retardation of curing and reduction in strength, can be prevented. Can be suppressed.
Therefore, the compounding 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, and still more preferably the weight of cement. Is 0.05 to 5.0% by weight. By such a compounding amount, various preferable effects such as a reduction in unit water amount, an increase in strength, and an improvement in durability can be obtained.

The cement composition can exhibit high dispersibility and dispersion holding performance even in a high water reduction rate region. And, even at low temperatures, sufficient initial dispersibility and viscosity reducing properties can be exhibited, and excellent workability can be obtained. Therefore, the above cement composition is effective as a raw material for various types of concrete by hardening.
Examples of concrete include ready-mixed concrete, concrete for secondary concrete products (precast concrete), centrifugal molding concrete, vibration compaction concrete, steam-cured concrete, and shotcrete. Furthermore, high fluidity such as medium fluidity concrete (concrete having a slump value of 22 to 25 cm), high fluidity concrete (concrete having a slump value of 25 cm or more and a slump flow value of 50 to 70 cm), self-compacting concrete, and self-leveling material Mortar or concrete which requires properties are also included.

[2-2-2. Gypsum composition]
A gypsum composition using gypsum as a hydraulic 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, the case where the hydraulic composition contains gypsum (a gypsum dispersant) will be described.

The gypsum is not particularly limited as long as it is a mineral mainly containing calcium sulfate (CaSO ₄ ). For example, calcium sulfate hemihydrate (CaSO ₄ .1 / 2H ₂ O: hemihydrate gypsum), calcium sulfate dihydrate _(CaSO 4 · _2H 2 O: gypsum), anhydrous calcium sulfate (CaSO _4: anhydrite) and the like. A common gypsum is hemihydrate gypsum. The gypsum may be either natural gypsum or chemical gypsum. With respect to natural gypsum, the place of origin and properties are not limited. Examples of the chemical gypsum include phosphogypsum, flue gas desulfurization gypsum, titanium gypsum, smelting gypsum, and hydrofluoric gypsum.

In the gypsum composition, the amount of the dispersant of the present invention, in terms of solid content, is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, based on the weight of the gypsum, It is more preferably at least 0.10% by weight. When the amount is 0.01% by weight or more, predetermined dispersibility is exhibited. The upper limit 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 not more than 5.00% by weight, it does not cause delay in hydration of gypsum, that is, delay in setting of gypsum, and thus functions as a dispersant excellent in workability.
Therefore, the compounding 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, and still more preferably the weight of gypsum. Is 0.10 to 1.00% by weight. By such a compounding amount, various preferable effects such as a reduction in the amount of water per unit, an increase in strength, and an improvement in durability are provided.

  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 at most 150% by weight, preferably at most 100% by weight. The gypsum composition may include gypsum, water, and commonly used additives other than the dispersant 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 materials, dental model materials, gypsum casting materials, etc. after hardening treatment such as heating and drying. it can.

[2-2-3. Other additives]
When the dispersant of the present invention is used as a dispersant for hydraulic composition, it is sufficient that the dispersant contains 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 go out. It is also possible to use in combination with other cement dispersants and other concrete additives. In the present specification, these are collectively referred to as “other additives”.

  As an active ingredient of another cement dispersant or an active ingredient of another concrete additive, for example, those listed below can be used. The active ingredient of the other cement dispersant and the active ingredient of the other additive for concrete may be used alone or in combination of two or more.

  Lignin sulfonic acid salt; polyol derivative; naphthalene sulfonic acid formalin condensate; melamine sulfonic acid formalin condensate; polystyrene sulfonic acid salt; amino sulfonic acid compounds such as aminoaryl sulfonic acid-phenol-formaldehyde condensate; -113419);

  Component (a) which is at least one of a copolymer of a polyalkylene glycol mono (meth) acrylate compound and a (meth) acrylic compound and a salt thereof, and a polyalkylene glycol mono (meth) allyl ether A component (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 compound with a maleic acid ester and a component (c) which is at least one of salts thereof (for example, JP-A-7-267705);

A component which is a component comprising a copolymer of a polyalkylene glycol ester of (meth) acrylic acid and (meth) acrylic acid (salt), and B component which is a component comprising a specific polyethylene glycol polypropylene glycol compound; A composition comprising a component C which is a component comprising a specific surfactant (for example, see Japanese Patent No. 2508113);
Composition comprising polyethylene (propylene) glycol ester of (meth) acrylic acid or polyethylene (propylene) glycol mono (meth) allyl ether, (meth) allylsulfonic acid (salt), and (meth) acrylic acid (salt) Vinyl copolymer containing units (for example, JP-A-62-216950);
Water-soluble vinyl copolymers obtained by aqueous polymerization of polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) allyl sulfonic acid (salt), and (meth) acrylic acid (salt) (for example, 1-222657);
Polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) allylsulfonic acid (salt) or p- (meth) allyloxybenzenesulfonic acid (salt), and (meth) acrylic acid (salt). Polymer (for example, see Japanese Patent Publication No. 5-36377);

Copolymer having a monomer unit formed from each of polyethylene glycol mono (meth) allyl ether and maleic acid (salt) (see, for example, JP-A-4-14956);
Structural units derived from polyethylene glycol ester of (meth) acrylic acid, structural units derived from (meth) allylsulfonic acid (salt), structural units derived from (meth) acrylic acid (salt), alkanediol mono (meth) A graft copolymer composed of constituent units containing a polymer block obtained by radical polymerization of an α, β-unsaturated monomer having an amide group in a molecule derived from acrylate or polyalkylene glycol mono (meth) acrylate. Polymer (for example, see JP-A-5-170501);

Polyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) acrylate, alkyl (meth) acrylate, (meth) acrylic acid (salt), and (meth) allylsulfonic acid (salt) or p- (meth) Water-soluble vinyl copolymer obtained by subjecting allyloxybenzenesulfonic acid (salt) to an aqueous radical copolymerization (for example, see JP-A-6-191918);
Polyethylene glycol monoallyl ether, maleic acid-based monomers, and copolymers obtained using monomers copolymerizable with these monomers (for example, see Japanese Patent Publication No. 58-38380);
A polyalkylene glycol mono (meth) acrylate monomer, a (meth) acrylic acid monomer, and a copolymer obtained by using a monomer copolymerizable with these monomers are alkalinized. Copolymer obtained by neutralization with a substance (for example, see Japanese Patent Publication No. 59-18338);

A polymer obtained using a polyalkylene glycol (meth) acrylate having a sulfo group and, if necessary, a monomer copolymerizable therewith, or a polymer obtained by neutralizing this with an alkaline substance (for example, And JP-A-62-119147);
Esterification reaction product of a copolymer of alkoxypolyalkylene glycol monoallyl ether and maleic anhydride with a polyalkylene oxide derivative having an alkenyl group at a terminal (for example, see JP-A-6-271347);
Esterification reaction product of a copolymer of alkoxypolyalkylene glycol monoallyl ether and maleic anhydride with a polyalkylene oxide derivative having a hydroxy group at a terminal (for example, see JP-A-6-298555);
Alkenyl ether-based monomers, unsaturated carboxylic acid-based monomers obtained by adding ethylene oxide or the like to specific unsaturated alcohols such as 3-methyl-3-buten-1-ol, and copolymerizable with these monomers Polycarboxylic acids (salts) such as copolymers composed of various monomers or salts thereof (see, for example, JP-A-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, Examples include a drying shrinkage reducing agent, a strength enhancer, an effect accelerator, an antifoaming agent, an AE agent, a separation reducing agent, a self-leveling agent, a rust preventive, a colorant, a fungicide 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 its salt (for example, sodium salt), polymethacrylic acid or its salt (for example, sodium salt), polymaleic acid or its salt (for example, sodium salt), acrylic acid / maleic acid copolymer or its salt ( Unsaturated carboxylic acid polymers such as sodium salts);
Nonionic cellulose ethers such as methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxyethylcellulose and hydroxypropylcellulose;

A polysaccharide derivative having an alkylated or hydroxyalkylated derivative of a polysaccharide (for example, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose) as a skeleton, wherein 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 to 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 glucans (which may be linear or branched, for example, curdlan, paramylon, pakiman, scleroglucan, laminaran) ;

Polyacrylamide; polyvinyl alcohol; starch; starch phosphate;
Sodium alginate; gelatin; copolymers of acrylic acid having an amino group in the molecule and quaternary compounds thereof.

  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.
Monosaccharide (eg, glucose, fructose, galactose, saccharose, xylose, apiose, ribose, isomerized sugar), disaccharide, trisaccharide, oligosaccharide (eg, dextrin), polysaccharide (eg, dextran), and / or at least any of these Saccharides such as sugar compositions (eg, molasses); sugar alcohols such as sorbitol; magnesium fluorosilicate; phosphoric acid and its salts or borate esters; aminocarboxylic acids and their salts; alkali-soluble proteins; Tannic acid; phenol; polyhydric alcohols such as glycerin; phosphonic acid, aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) This Et alkali metal salts of phosphonic acids and derivatives thereof such as alkaline earth metal salts.

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

Examples of the antifoaming 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 alkylene oxide adducts thereof; fatty acid defoamers such as oleic acid, stearic acid, and alkylene oxide adducts thereof Foaming agents; fatty acid ester-based antifoaming agents such as glycerin monoricinolate, alkenyl succinic acid derivatives, sorbitol monolaurate, sorbitol trioleate, and natural wax; alcohol-based antifoaming agents such as octyl alcohol, hexadecyl alcohol, acetylene alcohol, and glycols Foaming agents; amide-based antifoaming agents such as acrylate polyamines; phosphate-based antifoaming agents such as tributyl phosphate and sodium octyl phosphate; metal soap-based antifoaming agents such as aluminum stearate and calcium oleate; dimethyl silicone oil; Silicone pen Strike, silicone emulsions, organic modified polysiloxanes (dimethyl polysiloxane polyorganosiloxane), silicone anti-foaming agent such as fluorosilicone oil.

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

Other surfactants include, for example, the following.
Aliphatic monohydric alcohol having 6 to 30 carbon atoms in the molecule, such as octadecyl alcohol and stearyl alcohol; alicyclic monohydric 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 carbon atoms in a molecule such as dodecylamine Amines having atoms; polyalkylene oxide derivatives obtained by adding 10 mol or more of alkylene oxides such as ethylene oxide and propylene oxide to carboxylic acids having 6 to 30 carbon atoms in a molecule such as lauric acid and stearic acid; Having a sulfo group, which may have a substituent or an alkoxy group as a substituent Two phenyl groups are ether bonds, alkyl diphenyl ether sulfonic acid salts;

  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, oils and fats, silicone, paraffin, asphalt, wax, etc.

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

  Examples of the crack reducing agent include polyoxyalkyl ether.

  Examples of the expanding material include an ettringite-based material and a coal-based material.

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

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

  As the oxycarboxylic acid-based compound, an oxycarboxylic acid having 4 to 10 carbon atoms or a salt thereof is preferable. More specifically, gluconic acid, glucoheptonic acid, arabonic acid, malic acid, citric acid, and inorganic or organic salts thereof such as sodium, potassium, calcium, magnesium, ammonium, and triethanolamine are exemplified. 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, use a ligninsulfonate-based dispersant as a sulfonic acid-based dispersant having a sulfo group in the molecule, and use gluconic acid or a salt thereof as an oxycarboxylic acid-based compound. Is preferred.

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

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

  Hereinafter, the present invention will be described in detail with reference to examples. The following examples are provided for better illustration of the present invention and do not limit the present invention. In addition, the measuring method of a physical property value etc. is the measuring method described above, unless otherwise described. In Examples, unless otherwise specified, "%" indicates% by weight, and "parts" indicates parts by weight.

[Thermal decomposition point (° C)]: Measured by the following procedure using a thermogravimetric differential scanning calorimeter (TG-DTA) (trade name “STA7200”, manufactured by SII).
The granular composition or the target sample having a solid content of 10 g was dried and solidified at 105 ° C. About 10 mg of the solidified sample was heated from 50 ° C. to 600 ° C. at a rate of 10 ° C./min under a nitrogen atmosphere (nitrogen gas introduction rate: 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 obtained.
When the target sample is a polycarboxylic acid, it is dried and solidified at −20 ° C. for one day by a freeze dryer (trade name “FDU-1200”, manufactured by Tokyo Rika Kikai Co., Ltd.), or a blow dryer (trade name “ Drying and solidification at 105 ° C. for 1 day using a blower constant temperature incubator DKM600 (manufactured by Yamato Scientific Co., Ltd.) was employed. Otherwise, drying was performed at 180 ° C. using a spray dryer (trade name “TR120”, manufactured by Pris).

[Thermal weight loss rate (%)]: Measured by the following procedure using a thermogravimetric differential scanning calorimeter (TG-DTA) (trade name “STA7200”, manufactured by SII).
The granular composition or the target sample having a solid content of 10 g was dried and solidified at 105 ° C. About 10 mg of the solidified sample was heated from 50 ° C. to 600 ° C. at a rate of 10 ° C./min under a nitrogen atmosphere (nitrogen gas introduction rate: 100 mL / min). The weight reduction rate of the sample up to 600 ° C. was defined as the thermogravimetric reduction rate. The measurement was performed three times for each sample, and the average value was obtained.
When the target sample is a polycarboxylic acid, it is dried and solidified at −20 ° C. for one day by a freeze dryer (trade name “FDU-1200”, manufactured by Tokyo Rika Kikai Co., Ltd.), or a blow dryer (trade name “ Drying and solidification at 105 ° C. for 1 day using a blower constant temperature incubator DKM600 (manufactured by Yamato Scientific Co., Ltd.) was employed. Otherwise, drying was performed at 180 ° C. using a spray dryer (trade name “TR120”, manufactured by Pris).

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

[Example 1: Production of granular composition (1)]
In a glass reaction vessel equipped with a thermometer, a stirring device, a reflux device, and a dropping device, 229 g of water, 92 g of poly (ethylene oxide) monophenyl ether (number of moles of EO added: 50), and Sunflow RH (lignin sulfonate, Japan) 60 g of a 37% aqueous formaldehyde solution, 55 g of a 72% aqueous sulfuric acid solution, and 0.05 g of a defoaming agent Pronal 753 (manufactured by Toho Chemical Co., Ltd.) were charged, and the temperature of the reaction vessel was raised to 105 ° C. with 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. The mixture was filtered to remove gypsum produced by neutralization, thereby obtaining a lignin derivative containing a copolymer having a weight average molecular weight of 41,300. The reaction weight ratio of the ligninsulfonic acid compound [L] to the water-soluble compound [M] was [L] / [M] = 39/61, and the conversion of the water-soluble compound was 95%. The lignin derivative was dried at 180 ° C. using a spray dryer (trade name “TR120”, manufactured by Pris) to obtain the particulate composition (1) of the present invention as a solid.
The thermal decomposition point of the particulate composition (1) was 395 ° C., and the thermal weight loss rate was 68%.

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

[Example 3: Production of granular composition (3)]
Lignin sulfonic acid (trade name "Sanflow RH", manufactured by Nippon Paper Industries Co., Ltd.) having a shape of 175 g and a solid content of 70 g, and a polycarboxylic dispersant having a shape of 120 g and a solid content of 30 g (trade name "SF-500R") And FLRICK, and dried at 180 ° C. using a spray dryer (trade name “TR120”, manufactured by Pris) to obtain the particulate composition (3) of the present invention as a solid.
The weight ratio of the ligninsulfonic acid compound [L] to the water-soluble compound [M] was [L] / [M] = 70/30.
The thermal decomposition point of the particulate composition (3) was 236 ° C., and the thermal weight loss rate was 65%.

[Comparative Example 1: Production of control sample (1)]
Naphthalenesulfonic acid (trade name “Sanflow PS”, manufactured by Nippon Paper Industries) was dried at 180 ° C. using a spray dryer (trade name “TR120”, manufactured by Pris) to obtain a control sample (1) as a solid. Was.
The thermal decomposition point of the control sample (1) was 495 ° C., and the thermal weight loss rate was 20%.

[Comparative Example 2: Production of control sample (2)]
733 parts of water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a refluxing apparatus, a nitrogen inlet tube, and a dropping apparatus, and the reaction vessel was purged with nitrogen under stirring and heated to 100 ° C. under a nitrogen atmosphere. Then, a monomer aqueous solution obtained by mixing 21 parts of methacrylic acid, 30 parts of acrylic acid, 92 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide 25), and 70 parts of water, 3 parts of ammonium persulfate and 87 parts of water The mixed solution was continuously dropped into the reaction vessel maintained at 50 ° C. for 2 hours. 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% aqueous NaOH solution. The polycarboxylic acid-based dispersant in the liquid had a weight average molecular weight of 18,300 (Mw / Mn 1.6). 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. The thermal decomposition point of the control sample (2) was 405 ° C., and the thermal weight loss rate was 85%.

[Comparative Example 3: Production of control sample (3)]
A polycarboxylic acid-based dispersant (trade name “SF-500R”, manufactured by Floric) is dried at 105 ° C. for 1 day using a dryer (trade name “Blower constant temperature incubator DKM600”, manufactured by Yamato Kagaku). A control sample (3) was obtained as a solid.
The thermal decomposition point of the control sample (3) was 335 ° C., and the thermal weight loss rate was 88%.

[Comparative Example 4: Production of control sample (4)]
Lignin sulfonic acid (trade name “Sanflow RH”, manufactured by Nippon Paper Industries) was dried at 180 ° C. using a spray dryer (trade name “TR120”, manufactured by Pris) to obtain a control sample (4) as a solid. Was.
The thermal decomposition point of the control sample (4) was 310 ° C., and the thermal weight loss rate was 47%.

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

<Concrete test procedure and evaluation method: Examples 1 to 3, Comparative examples 1 to 4>
In a high temperature environment (40 ° C.) supposed in summer, coarse aggregate, fine aggregate and cement mixed as shown in Table 1 were charged and kneaded for 10 seconds by mechanical kneading with a forced twin-screw mixer. Next, water and the granular composition shown in Table 2 or the control sample (initial addition) were added in the amounts shown in Table 2, and after mixing for 90 seconds, a part of the concrete was discharged and a fresh concrete test ( An initial concrete evaluation was performed by performing a slump test JIS A 1101 (measuring the spread of fresh concrete as a flow value), and the prepared concrete was allowed to stand in a high-temperature environment (40 ° C.) for a predetermined period of time. After 15 minutes, 30 minutes, or 45 minutes), the above-mentioned fresh concrete test was carried out.

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

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

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

Claims (11)

Including a lignin sulfonic acid compound and a water-soluble compound,
A particulate composition having a thermogravimetric differential thermal analysis apparatus having a thermogravimetric reduction rate of 50 to 80%.   The granular composition according to claim 1, wherein a thermal decomposition point measured by a thermogravimetric differential thermal analyzer is 350 ° C or more and less than 400 ° C.   The granular composition according to claim 1 or 2, further comprising a lignin derivative that is a reaction product of a ligninsulfonic acid-based compound and a water-soluble compound.   The granular composition according to any one of claims 1 to 3, wherein the water-soluble compound is an aromatic water-soluble compound.   The granular composition according to claim 3, wherein the lignin derivative has an anionic functional group.   The granular composition according to any one of claims 3 to 5, wherein the lignin derivative has a polyalkylene oxide chain having an average alkylene oxide addition mole number of 25 or more.   In the lignin derivative, a reaction weight ratio ([L] / [M]) of the lignin sulfonic acid compound [L] and the aromatic water-soluble compound [M] is 1 to 99/99 to 1, The granular composition according to any one of claims 3 to 6.   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 4 to 7, comprising one or more.   The granular composition according to any one of claims 4 to 8, wherein the reaction rate of the aromatic water-soluble compound includes a lignin derivative having a reaction rate of 50% or more.   A dispersant comprising the granular composition according to any one of claims 1 to 9.   The dispersant according to claim 10, which is a muddy dispersant for oil field drilling or a dispersant for hydraulic compositions.