Powder composition and its uses

Abstract

To provide a powdery composition suitable for an additive for a hydraulic composition which has powder flowability equivalent to that of a conventional additive for a powdery hydraulic composition and excellent initial dispersibility or easy solidification in which the resulting solid agent has good solubility in a hydraulic composition and also has excellent dispersibility.SOLUTION: There is provided a powdery composition which comprises at least a component (A): a lignin derivative and a component (B): a copolymer constituted by a predetermined constitutional unit and satisfies at least one selected from an angle of repose of 50.0 degrees or less, a loose bulk density of 0.40 g / cm3 or less, an angle of collapse of 27.0 degrees or more and a particle diameter distribution of 100 μm or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a powdery composition and uses thereof, and more particularly to a powdery composition, a solid composition, an additive for a hydraulic composition, and a hydraulic composition. [Background technology]

[0002] Lignin is a natural polymeric substance found in trees, accounting for approximately 30% of wood. Lignin is found in large amounts in waste liquor from kraft pulp production (kraft pulp waste liquor) and waste liquor from sulfite pulp production (sulfite pulp waste liquor). In recent years, lignin has been attracting attention as a biomass resource from the perspective of reducing environmental impact.

[0003] Kraft lignin contained in kraft pulp waste liquor and lignosulfonic acid contained in sulfite pulp waste liquor have different physical properties and are used for various purposes. Furthermore, lignin derivatives obtained by sulfomethylating kraft lignin with sulfite and formaldehyde, lignin derivatives obtained by partially desulfonating lignosulfonic acid or salts of lignosulfonic acid, and purified lignin products obtained by ultrafiltration are widely used as lignin-based dispersants in a wide range of industrial fields, including dyes, cement, inorganic pigments, organic pigments, gypsum, coal-water slurries, pesticides, and ceramics.

[0004] Furthermore, with the aim of making effective use of lignin as a biomass resource, lignin derivatives have been proposed that can improve the dispersibility of various dispersed substances, regardless of their application, such as cement, dyes, and oil field drilling mud (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-240224 Summary of the Invention [Problem to be solved by the invention]

[0006] The solid lignin derivative has good powder properties, which makes it easy to handle when transporting or adding the agent. On the other hand, conventional lignin derivatives used as additives for hydraulic compositions do not provide a satisfactory dispersibility effect when added in small amounts, and in order to achieve initial dispersibility and dispersion retention in the hydraulic composition, it is necessary to add a large amount of the lignin derivative. Therefore, there is a demand for the development of an additive for powdery hydraulic compositions that has powder properties equivalent to those of conventional solid lignin derivatives and is excellent in initial dispersibility and dispersion retention.

[0007] In recent years, tablet-type additives have begun to emerge as a new product form for hydraulic composition additives. Tablet-type additives are easier to transport and work with than the liquid and powder products that have been the mainstream product forms for hydraulic composition additives up until now. However, the powder characteristics of conventional lignin derivatives used as additives for hydraulic compositions are not suitable for tableting, making them difficult to tablet, and even if tableting is possible, the solubility of the tablets in hydraulic compositions is poor, making it difficult to obtain satisfactory dispersibility. Therefore, there is a demand for the development of an additive for hydraulic compositions which can be easily tableted, and which has good solubility in the hydraulic composition and excellent dispersibility in the tablets.

[0008] The first object of the present invention is to provide a powdery composition suitable as an additive for hydraulic compositions, which has powder properties equivalent to those of conventional powdery additives for hydraulic compositions, such as lignin derivatives, and which has excellent initial dispersibility and dispersion retention properties.

[0009] A second object of the present invention is to provide a powdery composition suitable for producing a solid additive for hydraulic compositions, which is easy to solidify, has good solubility in hydraulic compositions, and also has excellent dispersibility. [Means for solving the problem]

[0010] As a result of extensive research into the above-mentioned problems, the present inventors have discovered a method for producing a lignin-based cellulose sieve containing at least a lignin derivative and a copolymer composed of predetermined structural units, the method having an angle of repose of 50.0° or less and a loose bulk density of 0.4 g / cm. 3 The inventors have found that a powdery composition that satisfies at least one of the following conditions can solve the above problems: a collapse angle of 27.0° or more; and a particle size distribution of 100 μm or more. This has led to the completion of the present invention.

[0011] That is, the present inventors provide the following invention. [1] Component (A): lignin derivative, and Component (B): A copolymer having at least two types of structural units selected from the group consisting of a structural unit (I) derived from a monomer represented by the following general formula (1), a structural unit (II) derived from a monomer represented by the following general formula (2), and a structural unit (III) derived from a monomer represented by the following general formula (3), The angle of repose is 50.0° or less, and the loose bulk density is 0.40 g / cm 3 A powdery composition that satisfies at least one of the following: a collapse angle of 27.0° or more; and a particle size distribution of 100 μm or more. [ka] (In the general formula (1), R 1 ~R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. p represents an integer of 0 to 2. q represents an integer of 0 to 1. A 1 O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. n represents an integer of 1 to 300. R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. [ka] (In the general formula (2), R 5 ~R 7 are each independently a hydrogen atom, a methyl group, or -(CH2) rCOOM 2 represents a group, provided that -(CH2) r COOM 2 When representing a group, -COOM 1 group or other -(CH2) r COOM 2 When an anhydride group is formed, the M 1 or M 2 does not exist. M 1 ~M 2 each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a substituted alkylammonium group, and r represents an integer of 0 to 2. [ka] (In the general formula (3), R 8 ~R 10 R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 11 represents a hydrocarbon group having 1 to 4 carbon atoms which may contain a heteroatom; and s represents an integer of 0 to 2. [2] The composition described in [1], having a collapse angle of 30.0° or more. [3] The composition according to [1] or [2], wherein the difference angle represented by the following mathematical formula (α) is 19.0° or less. Difference angle = Angle of repose - Angle of collapse (α) [4] Angle of repose is 50.0° or less and loose bulk density is 0.40 g / cm 3 The composition according to any one of [1] to [3], which is: [5] The composition according to [4], wherein the weight ratio of component (A) to component (B) ((A) / (B)) is 99:1 to 51:49. [6] The composition according to any one of [1] to [3], having a collapse angle of 27.0° or more and a particle size distribution of 100 μm or more. [7] The composition according to [6], wherein the weight ratio of component (A) to component (B) ((A) / (B)) is 50:50 to 1:99. [8] A solid composition, which is a solidified product of the composition according to any one of [1] to [7]. [9] The composition according to [8], wherein the solidified product is a solidified product of the composition according to [6] or [7].

[10] An additive for hydraulic compositions, comprising the composition according to any one of [1] to [9] as an active ingredient.

[11] A hydraulic composition comprising the additive according to

[10] .

[0012] As powdered additives and their uses, the following [1-1] to [1-3] are preferred. [1-1] Contains at least components (A) and (B), has an angle of repose of 50.0° or less, and a loose bulk density of 0.40 g / cm 3 The additive for a powdery hydraulic composition is as follows: [1-2] The powdery additive for hydraulic compositions according to [1-1], wherein the weight ratio of component (A) to component (B) ((A) / (B)) is 99:1 to 51:49. [1-3] A hydraulic composition comprising the powdery hydraulic composition additive according to [1-1] or [1-2].

[0013] As solid additives and their uses, the following [2-1] to [2-6] are preferred. [2-1] An additive for a solid hydraulic composition, which is a powder solidified product containing at least components (A) and (B) and having a collapse angle of 27.0° or more and a particle size distribution of 100 μm or more. [2-2] The additive for a solid hydraulic composition according to [2-1], having a collapse angle of 30.0° or more. [2-3] The additive for a solid hydraulic composition according to [2-1] or [2-2], wherein the difference angle represented by the following mathematical formula (α) is 19.0° or less. Difference angle = Angle of repose - Angle of collapse (α) [2-4] The additive for a solid hydraulic composition according to any one of [2-1] to [2-3], wherein the weight ratio of component (A) to component (B) ((A) / (B)) is 50:50 to 1:99. [2-5] A tablet-molded product comprising the additive for a solid hydraulic composition according to any one of [2-1] to [2-4]. [2-6] A hydraulic composition comprising the additive for a solid hydraulic composition according to any one of [2-1] to [2-4]. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a powdery composition suitable as an additive for hydraulic compositions, which has powder flowability equivalent to that of conventional powdery additives for hydraulic compositions, such as lignin derivatives, and is excellent in initial dispersibility and dispersion retention.

[0015] Furthermore, according to the present invention, it is possible to provide a powdery composition that is easy to solidify, and the resulting solidified product has good solubility in hydraulic compositions and also has excellent dispersibility, making it suitable for producing an additive for hydraulic compositions. DETAILED DESCRIPTION OF THE INVENTION

[0016] The present invention will be described in detail below based on preferred embodiments thereof. In this specification, the notation "AA to BB" means from AA to BB, and the notation "(meth)acrylic" means acrylic and / or methacrylic.

[0017] [1. Powder composition] The powdery composition of the present invention comprises component (A): a lignin derivative and component (B): a copolymer having a predetermined structural unit, and has an angle of repose of 50.0° or less and a loose bulk density of 0.40 g / cm 3 Hereinafter, at least one of the following conditions is satisfied: the collapse angle is 27.0° or more, and the particle size distribution is 100 μm or more.

[0018] [1-1. Physical Properties] The repose angle of the powdery composition is usually 50.0° or less, and preferably 48.0° or less. When the repose angle is 50.0° or less, the powder flowability and workability can be improved. The lower limit is usually 35.0° or more, but is not particularly limited. The angle of repose is a value measured using a powder tester (Powder Tester PT-X (manufactured by Hosokawa Micron Corporation)) on a sample prepared to have a solid content of 95% or more.

[0019] The loose bulk density of the powdered composition is typically 0.40 g / cm 3 or less, preferably 0.36 g / cm 3 The loose bulk density is 0.40 g / cm 3 When the ratio is equal to or less than this, excellent powder fluidity can be obtained, and the diffusibility and initial dispersibility when the hydraulic composition is poured are improved. The lower limit is usually 0.25 g / cm 3 The above is not particularly limited. The loose bulk density is a value measured using a powder tester (Powder Tester PT-X (manufactured by Hosokawa Micron Corporation)) on a sample whose solid content has been adjusted to 95% or more.

[0020] The disintegration angle of the powder composition is usually 27.0° or more, preferably 30.0° or more. When the disintegration angle is 27.0° or more, the powderability is reduced, and the composition can have excellent tablet suitability. Furthermore, when the solidified product obtained by solidifying the powder composition is added to a hydraulic composition, excellent disintegration properties can be obtained. The upper limit of the collapse angle is usually 45.0° or less, but is not particularly limited. The collapse angle is a value measured using a powder testing device (Powder Tester PT-X (manufactured by Hosokawa Micron Corporation)) on a sample whose solid content has been adjusted to 95% or more.

[0021] The particle size distribution of the powdered composition is usually 60 μm or more, 65 μm or more, 70 μm or more, or 100 μm or more, preferably 105 μm or more, more preferably 107 μm or more, and even more preferably 200 μm or more. When the particle size distribution is within the above range, especially 100 μm or more, the intermolecular interaction becomes strong and the cohesive force between particles is improved, which can improve tablet formability. The upper limit of the particle size distribution is usually 500 μm or less, but is not particularly limited. The particle size distribution was measured under dry conditions using a laser diffraction particle size distribution analyzer (Mastersizer 3000 (Malvern)) on 3 g of a powder sample, and the molecular weight distribution was obtained. The particle size distribution is expressed as particle size (μm) on the horizontal axis and volume (%) on the vertical axis, and is the value at which the cumulative distribution is 50%.

[0022] The difference angle of the powder composition is preferably 19.0° or less. When the difference angle is 19.0° or less, the powderability is reduced, resulting in excellent tablet suitability. Furthermore, when the solidified product is added to a hydraulic composition, excellent disintegrability can be obtained. The lower limit of the difference angle is usually 5.0° or more, but is not particularly limited. The angle difference is expressed by the following formula (α). Difference angle = Angle of repose - Angle of collapse (α) The difference angle is a value obtained by measuring the difference between the angle of repose and the angle of collapse using a powder property tester (Powder Tester PT-X (manufactured by Hosokawa Micron Corporation)) on a sample whose solid content has been adjusted to 95% or more.

[0023] [1-2. Component (A)] The powdery composition of the present invention contains at least component (A). Component (A) is a lignin derivative. The lignin derivative may be any compound having a lignin skeleton, and is preferably lignosulfonic acid or its salt, kraft lignin, or a combination thereof. Here, lignosulfonic acid refers to a compound in which at least a portion of lignin or a derivative thereof is substituted with a sulfonic acid (salt) group. Kraft lignin refers to a compound in which at least a portion of lignin or a derivative thereof has a thiol group. Component (A) may be one type of lignin derivative or a combination of two or more types.

[0024] It is difficult to uniformly specify the chemical structure of lignin derivatives by a general formula or the like because the lignin that constitutes the lignin derivatives has a very complex molecular structure.

[0025] When the powdery composition of the present invention is used as an additive for a powdery hydraulic composition, the content of component (A) is preferably 51% by weight or more, more preferably 55% by weight or more, and even more preferably 60% by weight or more, based on the total amount of components (A) and (B). When the content of component (A) is 51% by weight or more, a powdery product with good powder flowability can be obtained in good yield.

[0026] When the powdery composition of the present invention is used as an additive for a solid hydraulic composition, the content of component (A) is preferably less than 50% by weight, more preferably 45% by weight or less, based on the total amount of components (A) and (B). When the content of component (A) is less than 50% by weight, a solid product having good moldability can be obtained in good yield.

[0027] The lignin derivative may be prepared or may be a commercially available product. Here, an example of a method for preparing the lignin derivative is shown below. However, the lignin derivative is not limited to the one prepared by the following preparation method.

[0028] (Method for preparing lignin derivatives) Examples of methods for preparing lignin derivatives include a method in which lignocellulose raw materials are subjected to a sulfite treatment, preferably a method in which lignocellulose raw materials are subjected to a sulfite cooking treatment.

[0029] The lignocellulose raw material is not particularly limited as long as it contains lignocellulose in the construct, and examples thereof include pulp raw materials such as wood and non-wood. Examples of wood include coniferous trees such as Yezo spruce, red pine, cedar, and cypress, and broad-leaved trees such as white birch and beech. The age and location of the wood do not matter. Therefore, wood harvested from trees of different ages or from different locations on a tree may be combined and used. Examples of non-wood materials include bamboo, kenaf, reeds, and rice. The lignocellulose raw material may be one of these materials or a combination of two or more of them.

[0030] The sulfite treatment can be carried out by contacting at least one of sulfurous acid and a sulfite salt with a lignocellulosic raw material to obtain an intermediate product. The conditions for the sulfite treatment are not particularly limited, and may be any conditions that allow the introduction of sulfonic acid (salt) groups to the α-carbon atoms of the side chains of lignin contained in the lignocellulosic raw material.

[0031] The sulfite treatment is preferably carried out by sulfite cooking, which allows for more quantitative sulfonation of lignin in the lignocellulosic raw material. The sulfite cooking method is a method in which lignocellulosic raw materials are reacted at high temperatures in a solution of at least one of sulfurous acid and sulfite salts (e.g., an aqueous solution: cooking liquor). This method has been established and is used industrially as a method for producing sulfite pulp. Therefore, by carrying out the sulfite treatment using the sulfite cooking method, it is possible to improve the economy and ease of implementation.

[0032] When sulfite cooking is carried out, examples of sulfite salts include magnesium salts, calcium salts, sodium salts, and ammonium salts.

[0033] The concentration of sulfurous acid (SO2) in the solution of at least one of sulfurous acid and sulfite is not particularly limited, but the ratio of weight (g) of SO2 to 100 mL of solution is preferably 1 g / 100 mL or more.

[0034] The pH value for the sulfite treatment is not particularly limited, but is preferably 10 or less, and more preferably 5 or less when sulfite cooking is performed. The lower limit of the pH value is preferably 0.1 or more, and more preferably 0.5 or more when sulfite cooking is performed. The pH value for the sulfite treatment is preferably 0.1 to 10, and more preferably 0.5 to 5 when sulfite cooking is performed.

[0035] The temperature for the sulfite treatment is not particularly limited, but is preferably 170° C. or lower, and the lower limit is preferably 70° C. or higher.

[0036] In the sulfite treatment, it is preferable to add a compound that supplies a counter cation (salt). By adding a compound that supplies a counter cation, the pH value during the sulfite treatment can be maintained constant. Examples of compounds that supply counter cations include MgO, Mg(OH)2, CaO, Ca(OH)2, CaCO3, NH3, NH4OH, NaOH, NaHCO3, and Na2CO3. The counter cation is preferably a sodium ion, a magnesium ion, or a calcium ion. The inorganic salts are usually contained in the lignin derivative in an amount of about 3 to 20%, and can be measured by a known method.

[0037] When a solution of at least one of sulfurous acid and sulfite salts is used in the sulfite treatment, the solution may contain, in addition to SO2, the above-mentioned counter cations (salts) and digestion penetrants (e.g., cyclic ketone compounds such as anthraquinone sulfonates, anthraquinone, and tetrahydroanthraquinone) as needed.

[0038] There are no limitations on the equipment used for the sulfite treatment, and for example, commonly known dissolving pulp manufacturing equipment can be used.

[0039] The intermediate product can be separated from the solution of at least one of sulfurous acid and sulfite salts by a conventional method, such as the method for separating the sulfite cooking effluent after sulfite cooking.

[0040] The intermediate composition is then washed and dehydrated to obtain a sulfite-treated product. By washing and dehydrating, components contained in the intermediate composition that cannot be completely removed by the sulfite treatment can be removed.

[0041] Washing may be carried out in the same manner as for unbleached sulfite pulp obtained by sulfite cooking. Washing may be a single-stage washing or a multi-stage washing. Multi-stage washing allows for sufficient washing. When multi-stage washing is carried out, dehydration may be carried out each time, or may be carried out only in some of the stages. Washing is usually performed using a washer. The type of washer used for washing is not particularly limited. Examples include a displacement washing type washer and a dilution and dehydration washing type washer.

[0042] The dehydration can be carried out under ordinary conditions, for example, in the same manner as in the dehydration of unbleached sulfite pulp after washing obtained in the sulfite cooking method. Dehydration is usually performed using a dehydrator. The type of dehydrator used for dehydration is not particularly limited. Examples include a drum-type squeeze dehydrator, a rotary press, and a continuous squeeze dehydrator.

[0043] Thereafter, the sulfite-treated product is washed and dehydrated as necessary, and then separated and purified to obtain the desired lignin derivative. Examples of the separation and purification include an alkaline oxidation treatment step and an ultrafiltration treatment step.

[0044] In the case of alkali oxidation treatment, after the sulfite-treated product is subjected to alkali oxidation treatment, the insoluble matter can be centrifuged and recovered as a supernatant.

[0045] The alkaline oxidation treatment can be carried out by placing the sulfite-treated product under alkaline conditions. Placing the product under alkaline conditions usually means placing the product in an aqueous solution with a pH of 8 or higher, preferably a pH of 9 or higher. The upper limit of the pH is usually 14.

[0046] In the alkaline oxidation treatment, an alkaline substance is usually brought into contact with the sulfite-treated product. The alkaline substance is not particularly limited, but examples thereof include calcium hydroxide, magnesium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and ammonia. Among these, sodium hydroxide is preferred. The alkaline substances may be used alone or in combination of two or more.

[0047] Examples of methods for contacting the sulfite-treated product with an alkaline substance include a method in which a dispersion or solution (e.g., an aqueous dispersion or aqueous solution) of the sulfite-treated product is prepared and the alkaline substance is added to the dispersion or solution, and a method in which a solution or dispersion (e.g., an aqueous dispersion or aqueous solution) of the alkaline substance is added to the sulfite-treated product.

[0048] The temperature of the alkaline oxidation treatment is not particularly limited, but is preferably 40° C. or higher, more preferably 60° C. or higher, and the upper limit is preferably 150° C. or lower.

[0049] The amount of alkaline substance in the alkaline oxidation treatment is preferably 0.5 to 20 wt %, more preferably 1.0 to 15 wt %, based on the weight of the solid content of the sulfite-treated product, or, when preparing an aqueous solution or dispersion by dispersing the alkali-treated extract in an aqueous solvent (e.g., water), based on the weight of the aqueous solution or dispersion.

[0050] The time for the alkaline oxidation treatment is not particularly limited, but is preferably 0.1 hours or more, more preferably 0.5 hours or more, and the upper limit is preferably 10 hours or less, more preferably 6 hours or less.

[0051] Prior to the alkaline oxidation treatment, the sulfite-treated product may be dissolved, dispersed, or its concentration adjusted (prepared as a solution or dispersion in an aqueous solvent such as water) as needed. Dispersion can be carried out by passing the product through a disc refiner, adding it to a mixer or disperser, or by kneading it. The concentration can be adjusted, for example, using an aqueous solvent such as water.

[0052] The ultrafiltration process can be performed using an ultrafiltration membrane (hereinafter also referred to as "UF membrane"). Known UF membranes can be used. Examples include hollow fiber membranes, spiral membranes, tubular membranes, and flat membranes. UF membranes can be made of known materials, such as cellulose acetate, aromatic polyamide, polyvinyl alcohol, polysulfone, polyvinylidene fluoride, polyethylene, polyacrylonitrile, and ceramic. The UF membranes may be commercially available.

[0053] The molecular weight cutoff of the UF membrane is preferably 5,000 to 30,000, more preferably 10,000 to 25,000, and even more preferably 15,000 to 23,000. Using a UF membrane with a molecular weight cutoff of 5,000 or more can prevent the separation rate of black liquor from becoming excessively slow. Furthermore, using a UF membrane with a molecular weight cutoff of 30,000 or less can prevent lignin from becoming unable to be separated from black liquor.

[0054] The concentration ratio by ultrafiltration using a UF membrane can be set arbitrarily. That is, the ultrafiltration can be stopped when the amount of concentrate flowing out reaches a desired amount.

[0055] The temperature of the black liquor during ultrafiltration is not particularly limited, and is preferably 20 to 80°C, and more preferably 20 to 70°C in consideration of the heat resistance of the UF membrane material. The pH value of the black liquor during the ultrafiltration treatment is preferably 2 to 11. The solids concentration (w / w) of the black liquor during ultrafiltration is preferably 2 to 30%, more preferably 5 to 15%.

[0056] [1-3. Ingredient (B)] The powdery composition of the present invention contains at least component (B). Component (B) is a copolymer having at least two types of structural units selected from the group consisting of structural unit (I) derived from a monomer represented by general formula (1), structural unit (II) derived from a monomer represented by general formula (2), and structural unit (III) derived from a monomer represented by general formula (3). The copolymer of component (B) may be one type or a combination of two or more types.

[0057] When the powdery composition of the present invention is used as an additive for a powdery hydraulic composition, the content of component (B) is preferably 1 to 49% by weight, more preferably 1 to 45% by weight, and even more preferably 1 to 40% by weight, based on the total amount of components (A) and (B). When the content of component (B) is within this range, a powdery product with better water solubility can be obtained after drying.

[0058] When the powdery composition of the present invention is used as a raw material for an additive for a solid hydraulic composition, the content of component (B) is preferably 50 to 90% by weight, more preferably 55 to 90% by weight, based on the total amount of components (A) and (B). When the content of component (B) is within this range, a solid product having good water solubility can be obtained after drying. Details of each constituent unit are described below.

[0059] (Structural unit (I)) The structural unit (I) is a structural unit derived from a monomer represented by the following general formula (1).

[0060] [ka]

[0061] In general formula (1), R 1 ~R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. p represents an integer of 0 to 2. q represents an integer of 0 to 1. A 1 O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. n represents an integer of 1 to 300. R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. R 1 is preferably a hydrogen atom. 2 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. 3 is preferably a hydrogen atom.

[0062] In general formula (1), A 1O may be the same or different and represent an oxyalkylene group having 2 to 18 carbon atoms. Examples of the oxyalkylene group (alkylene glycol unit) include an oxyethylene group (ethylene glycol unit), an oxypropylene group (propylene glycol unit), and an oxybutylene group (butylene glycol unit). Of these, an oxyethylene group and an oxypropylene group are preferred.

[0063] The above-mentioned "may be the same or different" means that A 1 If multiple Os are included (n is 2 or more), each A 1 This means that O may be the same oxyalkylene group or may be different (two or more types) oxyalkylene groups. 1 When a plurality of O's are contained, an embodiment in which two or more oxyalkylene groups selected from the group consisting of an oxyethylene group, an oxypropylene group, and an oxybutylene group are present in combination can be mentioned. More specifically, an embodiment in which an oxyethylene group and an oxypropylene group are present in combination, or an oxyethylene group and an oxybutylene group are present in combination is preferred, and an embodiment in which an oxyethylene group and an oxypropylene group are present in combination is more preferred. In an embodiment in which different oxyalkylene groups are present, the addition of two or more types of oxyalkylene groups may be block-like addition or random addition.

[0064] In general formula (1), n ​​is the average number of moles of oxyalkylene groups added, and represents an integer of 1 to 300. n is preferably 1 to 200. The average number of moles added means the average value of the number of moles of oxyalkylene groups added to 1 mole of the monomer.

[0065] In general formula (1), R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. 4 R is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and even more preferably a hydrogen atom or a methyl group. 4If the number of carbon atoms is within this range, the number of carbon atoms will not be too large, and therefore when used as an additive for a hydraulic composition, good dispersibility is exhibited.

[0066] Examples of methods for producing the monomer represented by general formula (1) include a method in which 1 to 300 moles of alkylene oxide are added to unsaturated alcohols such as allyl alcohol, methallyl alcohol, and 3-methyl-3-buten-1-ol. Monomers that can be produced by this method include, for example, (poly)ethylene glycol allyl ether, (poly)ethylene glycol methallyl ether, (poly)ethylene glycol 3-methyl-3-butenyl ether, (poly)ethylene glycol (poly)propylene glycol allyl ether, (poly)ethylene glycol (poly)propylene glycol methallyl ether, (poly)ethylene (poly)propylene glycol allyl ether, (poly)ethylene (poly)propylene glycol methallyl ether, (poly)ethylene (poly)propylene glycol 3-methyl-3-butenyl ether, (poly)ethylene (poly)butylene glycol allyl ether, (poly)ethylene (poly)butylene glycol methallyl ether, and (poly)ethylene (poly). Examples include butylene glycol 3-methyl-3-butenyl ether, methoxy(poly)ethylene glycol allyl ether, methoxy(poly)ethylene glycol methallyl ether, methoxy(poly)ethylene glycol 3-methyl-3-butenyl ether, methoxy(poly)ethylene (poly)propylene glycol allyl ether, methoxy(poly)ethylene (poly)propylene glycol methallyl ether, methoxy(poly)ethylene (poly)propylene glycol 3-methyl-3-butenyl ether, methoxy(poly)ethylene (poly)butylene glycol allyl ether, methoxy(poly)ethylene (poly)butylene glycol methallyl ether, and methoxy(poly)ethylene (poly)butylene glycol 3-methyl-3-butenyl ether. Among these, from the viewpoint of the balance between hydrophilicity and hydrophobicity, (poly)ethylene glycol (meth)allyl ether, (poly)ethylene glycol (poly)propylene glycol (meth)allyl ether, (poly)ethylene (poly)propylene glycol (meth)allyl ether, (poly)ethylene glycol 3-methyl-3-butenyl ether, and (poly)ethylene (poly)propylene glycol 3-methyl-3-butenyl ether are preferred.

[0067] Another example of a method for producing the monomer represented by general formula (1) is the esterification of an unsaturated monocarboxylic acid such as (meth)acrylic acid with a (poly)alkylene glycol such as (poly)ethylene glycol, (poly)ethylene (poly)propylene glycol, (poly)ethylene (poly)butylene glycol, methoxy(poly)ethylene glycol, methoxy(poly)ethylene (poly)propylene glycol, or methoxy(poly)ethylene (poly)butylene glycol. Monomers that can be produced by this method include, for example, (poly)alkylene glycol (meth)acrylates such as (poly)ethylene glycol (meth)acrylate, (poly)ethylene (poly)propylene glycol (meth)acrylate, and (poly)ethylene (poly)butylene glycol (meth)acrylate; and methoxy(poly)alkylene glycol (meth)acrylates such as (poly)alkylene glycol (meth)acrylates such as methoxy(poly)ethylene glycol (meth)acrylate, methoxy(poly)ethylene (poly)propylene glycol (meth)acrylate, and methoxy(poly)ethylene (poly)butylene glycol (meth)acrylate. Among these, (poly)alkylene glycol (meth)acrylate and methoxy(poly)ethylene glycol (meth)acrylate are preferred, and methoxy(poly)ethylene glycol (meth)acrylate is more preferred.

[0068] When the copolymer has the structural unit (I), it may have only one type of structural unit (I), or it may have two or more types of structural units (I) derived from different monomers.

[0069] (Structural unit (II)) The structural unit (II) is a structural unit derived from a monomer represented by the following general formula (2).

[0070] [ka]

[0071] In general formula (2), R 5 ~R 7 are each independently a hydrogen atom, a methyl group, or -(CH2) r COOM 2 represents a group, provided that -(CH2) r COOM 2 When representing a group, -COOM 1 group or other -(CH2) r COOM 2 When an anhydride group is formed, the M 1 or M 2 does not exist. M 1 ~M 2 each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a substituted alkylammonium group, and r represents an integer of 0 to 2. R 5 is preferably a hydrogen atom. 6 is a hydrogen atom, a methyl group or (CH2) r COOM 2 is preferred. 7 is preferably a hydrogen atom.

[0072] M 1 and M 2 M may be the same or different and are a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a substituted alkylammonium group. 1 , M 2 are preferably a hydrogen atom, an alkali metal, or an alkaline earth metal.

[0073] r represents an integer of 0 to 2. r is preferably 0 or 1, and more preferably 0.

[0074] Examples of the monomer represented by general formula (2) include unsaturated monocarboxylic acid monomers and unsaturated dicarboxylic acid monomers. Specific examples of unsaturated monocarboxylic acid monomers include acrylic acid, methacrylic acid, crotonic acid, etc., and their monovalent metal salts, ammonium salts, and organic amine salts. Specific examples of unsaturated dicarboxylic acids include maleic acid, itaconic acid, citraconic acid, fumaric acid, etc., and their monovalent metal salts, ammonium salts, and organic amine salts, or their anhydrides. Preferred examples of the monomer represented by general formula (2) include acrylic acid, methacrylic acid, and maleic acid.

[0075] When the copolymer has the structural unit (II), it may have only one type of structural unit (II), or it may have two or more types of structural unit (II) derived from different monomers.

[0076] (Structural unit (III)) The structural unit (III) is a structural unit derived from a monomer represented by the following general formula (3).

[0077] [ka]

[0078] In general formula (3), R 8 ~R 10 R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 11 represents a hydrocarbon group having 1 to 4 carbon atoms which may contain a heteroatom; s represents an integer of 0 to 2; Examples of alkyl groups having 1 to 3 carbon atoms include R 1 ~R 3 Similar to the example in R 8 is preferably a hydrogen atom. 9 is preferably a hydrogen atom. 10 is preferably a hydrogen atom.

[0079] In general formula (3), R 11 represents a hydrocarbon group having 1 to 4 carbon atoms which may contain a heteroatom. The number of carbon atoms is preferably 1 to 3, more preferably 2 to 3, and even more preferably 3. Examples of heteroatoms include an oxygen atom, a nitrogen atom, a phosphorus atom, and a silicon atom. Of these, an oxygen atom is preferred. Examples of hydrocarbon groups having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, an isobutyl group, and a sec-butyl group. R 11 The number of heteroatoms contained in may be 1 or may be 2 or more. When two or more heteroatoms are contained, the respective heteroatoms may be the same or different from each other.

[0080] R 11 is preferably a hydrocarbon group containing a heteroatom and having 1 to 4 carbon atoms, more preferably a hydrocarbon group containing an oxygen atom and having 1 to 4 carbon atoms. Examples of such groups include a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, and a glyceryl group. Of these, a 2-hydroxyethyl group and a 2-hydroxypropyl group are preferred.

[0081] In the general formula (3), s represents an integer of 0 to 2. s is preferably 0.

[0082] Examples of the monomer represented by general formula (3) include monoesters of unsaturated monocarboxylic acids. Examples of unsaturated monocarboxylic acid monoesters include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glyceryl (meth)acrylate. Among these, 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate are preferred.

[0083] When the copolymer has the structural unit (III), it may have only one type of structural unit (III), or it may have two or more types of structural unit (III) derived from different monomers.

[0084] When the copolymer has at least two structural units selected from the group consisting of the structural units (I) to (III), compatibility with component (A) is improved, and component (A) can be more uniformly dispersed in the cement composition.

[0085] The copolymer may contain a structural unit (IV) in addition to the structural units (I) to (III).

[0086] (Structural unit (IV)) The structural unit (IV) is a structural unit derived from a monomer copolymerizable with the monomers represented by the above general formulas (1) to (3). The monomers copolymerizable with the monomers represented by the above general formulas (1) to (3) are structurally distinct from the monomers represented by the above general formulas (1) to (3). The monomer that constitutes the structural unit (IV) is not particularly limited, and examples thereof include the following monomers: These monomers can be used alone or in combination of two or more.

[0087] A monomer represented by general formula (IV-1):

[0088] [ka]

[0089] Examples of the monomer represented by general formula (IV-1) include 3- and 3'-allyl-substituted bisphenols such as 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, and 4,4'-dihydroxydiphenylsulfone.

[0090] A monomer represented by general formula (IV-2):

[0091] [ka]

[0092] Examples of the monomer represented by the general formula (IV-2) include 3-allyl-substituted bisphenols such as 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, and 4,4'-dihydroxydiphenylsulfone.

[0093] A monomer represented by general formula (IV-3):

[0094] [ka]

[0095] An example of the monomer represented by the general formula (IV-3) is allylphenol.

[0096] Half esters and diesters of unsaturated dicarboxylic acids, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic acid, with alcohols having 1 to 30 carbon atoms;

[0097] Half amides and diamides of the above unsaturated dicarboxylic acids with amines having 1 to 30 carbon atoms;

[0098] half esters, half amides, diesters and diamides of (poly)oxyalkylene alkyl ethers or (poly)oxyalkylene alkylamines obtained by adding 1 to 500 moles of alkylene oxide having 2 to 18 carbon atoms to the above alcohols or amines, and the above unsaturated dicarboxylic acids;

[0099] Half esters and diesters of the above unsaturated dicarboxylic acids with glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 moles of addition of such glycols;

[0100] Half amides of maleamic acid and glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 moles of such glycols added;

[0101] (poly)ethylene glycol mono(meth)acrylate, (poly)propylene glycol mono(meth)acrylate, (poly)butylene glycol mono(meth)acrylate, etc., in which 1 to 500 moles of alkylene oxide having 2 to 18 carbon atoms are added to unsaturated monocarboxylic acids such as (meth)acrylic acid (however, excluding monomers represented by general formulas (1) to (3));

[0102] (poly)alkylene glycol di(meth)acrylates such as triethylene glycol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and (poly)ethylene glycol (poly)propylene glycol di(meth)acrylate;

[0103] polyfunctional (meth)acrylates such as hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trimethylolpropane di(meth)acrylate;

[0104] (Poly)alkylene glycol dimaleates such as triethylene glycol dimaleate and polyethylene glycol dimaleate;

[0105] unsaturated sulfonic acids such as vinyl sulfonate, (meth)allyl sulfonate, 2-(meth)acryloxyethyl sulfonate, 3-(meth)acryloxypropyl sulfonate, 3-(meth)acryloxy-2-hydroxypropyl sulfonate, 3-(meth)acryloxy-2-hydroxypropyl sulfophenyl ether, 3-(meth)acryloxy-2-hydroxypropyloxysulfobenzoate, 4-(meth)acryloxybutyl sulfonate, (meth)acrylamidomethyl sulfonic acid, (meth)acrylamidoethyl sulfonic acid, 2-methylpropanesulfonic acid (meth)acrylamide, and styrenesulfonic acid, as well as their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts;

[0106] amides of unsaturated monocarboxylic acids and amines having 1 to 30 carbon atoms, such as methyl (meth)acrylamide;

[0107] vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene;

[0108] Alkanediol mono(meth)acrylates such as 1,5-pentanediol mono(meth)acrylate and 1,6-hexanediol mono(meth)acrylate (excluding monomers represented by general formula (3));

[0109] Dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, and 2-chloro-1,3-butadiene;

[0110] unsaturated amides such as (meth)acrylamide, (meth)acrylalkylamide, N-methylol(meth)acrylamide, and N,N-dimethyl(meth)acrylamide;

[0111] Unsaturated cyanides such as (meth)acrylonitrile and α-chloroacrylonitrile;

[0112] unsaturated esters such as vinyl acetate and vinyl propionate;

[0113] Unsaturated amines such as aminoethyl (meth)acrylate, methylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, and vinylpyridine (excluding monomers represented by general formula (3));

[0114] Divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate;

[0115] Allyl compounds such as (meth)allyl alcohol and glycidyl (meth)allyl ether;

[0116] Vinyl ethers or allyl ethers such as methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono(meth)allyl ether, and polyethylene glycol mono(meth)allyl ether (excluding the monomer represented by general formula (1));

[0117] Siloxane derivatives such as polydimethylsiloxane propylaminomaleic acid, polydimethylsiloxane aminopropylene aminomaleic acid, polydimethylsiloxane-bis-(propylaminomaleic acid), polydimethylsiloxane-bis-(dipropyleneaminomaleic acid), polydimethylsiloxane-(1-propyl-3-acrylate), polydimethylsiloxane-(1-propyl-3-methacrylate), polydimethylsiloxane-bis-(1-propyl-3-acrylate), and polydimethylsiloxane-bis-(1-propyl-3-methacrylate) (however, excluding the monomer represented by general formula (3)).

[0118] The copolymer may have only one type of structural unit (IV), or may have two or more types of structural unit (IV) derived from different monomers.

[0119] In the copolymer, each of the structural units (I) to (IV) may be a structural unit composed of one type of monomer, or may be a structural unit composed of a combination of two or more types of monomers. Among these, the copolymer is preferably a copolymer that is a combination of the structural unit (I) and the structural unit (II), or a copolymer that is a combination of the structural units (I) to (III).

[0120] (Method for preparing copolymer) The copolymer can be prepared by copolymerizing the respective predetermined monomers by a known method, such as polymerization in a solvent or bulk polymerization.

[0121] Examples of solvents used in polymerization in a solvent include water, lower 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. From the viewpoint of the solubility of the raw material monomers and the resulting copolymer, it is preferable to use at least one of water and a lower alcohol as the solvent, and it is more preferable to use water.

[0122] When the polymerization reaction is carried out in a solvent, each monomer and the polymerization initiator may be continuously added dropwise to a reaction vessel, or a mixture of each monomer and the polymerization initiator may be continuously added dropwise to a reaction vessel. Alternatively, a solvent may be charged into a reaction vessel, and a mixture of the monomers and the solvent and a polymerization initiator solution may be continuously added dropwise to the reaction vessel, or a part or all of the monomers may be charged into a reaction vessel, and the polymerization initiator may be continuously added dropwise.

[0123] The polymerization initiator that can be used in the polymerization reaction is not particularly limited. Examples of polymerization initiators that can be used when carrying out a polymerization reaction in an aqueous solvent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; and water-soluble peroxides such as t-butyl hydroperoxide and hydrogen peroxide. In this case, an accelerator such as L-ascorbic acid, sodium bisulfite, or Mohr's salt may be used in combination. Examples of polymerization initiators that can be used when carrying out a polymerization reaction in an organic solvent such as a lower alcohol, aromatic hydrocarbon, aliphatic hydrocarbon, ester, or ketone include peroxides such as benzoyl peroxide and lauryl peroxide; hydroperoxides such as cumene peroxide; and azo compounds such as azobisisobutyronitrile. In this case, an accelerator such as an amine compound may be used in combination. The polymerization initiator that can be used when carrying out a polymerization reaction in a water-lower alcohol mixed solvent may be appropriately selected from the above-mentioned polymerization initiators or combinations of polymerization initiators and accelerators. The polymerization temperature varies depending on the polymerization conditions such as the type of solvent and polymerization initiator used, but is usually 40 to 120°C.

[0124] In the polymerization reaction, the molecular weight can be adjusted, if necessary, using a chain transfer agent. Examples of the chain transfer agent include known thiol compounds such as mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, and 2-mercaptoethanesulfonic acid; phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.); sulfurous acid, hydrogen sulfite, dithionous acid, metabisulfite, and salts thereof (sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.), lower oxides or salts thereof. These chain transfer agents may be used alone or in combination of two or more.

[0125] When polymerization is performed in an aqueous solvent to obtain a copolymer, the pH during the polymerization reaction is usually strongly acidic due to the influence of the monomers having unsaturated bonds. However, this may be adjusted to an appropriate pH. If pH adjustment is required during the polymerization reaction, the pH can be adjusted using an acidic substance such as phosphoric acid, sulfuric acid, nitric acid, alkyl phosphoric acid, alkyl sulfuric acid, alkyl sulfonic acid, or (alkyl)benzenesulfonic acid. Among these acidic substances, phosphoric acid is preferred because of its pH buffering effect. However, to eliminate the instability of the ester bonds in ester-based monomers, the polymerization reaction is preferably performed at a pH of 2 to 7. There are no particular limitations on the alkaline substance that can be used to adjust the pH; alkaline substances such as NaOH and Ca(OH)2 are commonly used. The pH adjustment may be performed on the monomers before the polymerization reaction or on the copolymer solution after the polymerization reaction. Alternatively, a portion of the alkaline substance may be added before the polymerization reaction to perform polymerization, and then the pH of the copolymer may be further adjusted (e.g., to a pH of 3 to 7).

[0126] The copolymer can be prepared as a liquid. Examples of liquid solvents include aqueous solvents. Examples of aqueous solvents include water, alcohols having 1 to 6 carbon atoms (ethyl alcohol, methyl alcohol, ethylene glycol, diethylene glycol, etc.), and ketones having 1 to 6 carbon atoms (methyl isobutyl ketone, acetone, etc.). These aqueous solvents may be used alone or in combination of two or more. Water is preferred as the aqueous solvent. The lower limit of the solid content concentration in the copolymer is preferably 5% by weight or more, more preferably 15% by weight or more, and the upper limit is preferably 70% by weight or less, more preferably 65% ​​by weight or less.

[0127] Component (B) may contain at least one monomer selected from the group consisting of the above general formulas (1) to (3), which is a raw material for the copolymer. When obtaining the copolymer, treatments such as removal of the reaction solvent, concentration, purification, etc. may be carried out as necessary. These treatment methods may be conventionally known methods.

[0128] The lower limit of the weight-average molecular weight (Mw) of the copolymer is preferably 5,000 or more, more preferably 7,000 or more, and even more preferably 10,000 or more. By using a copolymer having this weight-average molecular weight as component (B), the dispersibility of the cement composition can be sufficiently exhibited when it is used as a cement composition dispersant. Therefore, fluidity or workability can be improved. The upper limit of the weight-average molecular weight is preferably 60,000 or less, more preferably 45,000 or less, and even more preferably 30,000 or less. By using a copolymer having this weight-average molecular weight as component (B), the aggregation of particles in the cement composition can be suppressed, and workability can be improved. The weight-average molecular weight is preferably 5,000 to 60,000, more preferably 7,000 to 45,000, and even more preferably 10,000 to 30,000.

[0129] The lower limit of the molecular weight distribution (Mw / Mn) of the copolymer is preferably 1.0 or more, more preferably 1.2 or more. The upper limit is preferably 3.0 or less, more preferably 2.5 or less. The molecular weight distribution is preferably in the range of 1.0 to 3.0, more preferably 1.2 to 3.0, and even more preferably 1.2 to 2.5.

[0130] The weight-average molecular weight can be measured by a known method using gel permeation chromatography (GPC) in terms of polyethylene glycol. The measurement conditions for GPC are not particularly limited, and the following conditions can be mentioned, for example. The weight-average molecular weight in the examples below is a value measured under these conditions. Measuring device: Tosoh Columns used: Shodex Column OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ Eluent: 0.05 mM sodium nitrate / acetonitrile 8 / 2 (v / v) Standard material: polyethylene glycol (manufactured by Tosoh Corporation or GL Sciences Co., Ltd.) Detector: Differential refractometer (Tosoh Corporation) Calibration curve: polyethylene glycol standard

[0131] When the powdery composition of the present invention is used as an additive for a powdery hydraulic composition, the weight ratio of component (A) to component (B) ((A) / (B)) is preferably 99:1 to 51:49, more preferably 90:10 to 55:45, and even more preferably 80:20 to 60:40. When the weight ratio of component (A) to component (B) ((A) / (B)) satisfies the above range, sufficient initial dispersibility can be exhibited while maintaining good powderability.

[0132] When the powdery composition of the present invention is used as an additive for a solid hydraulic composition, the weight ratio of component (A) to component (B) ((A) / (B)) is preferably 1:99 to 50:50, more preferably 10:90 to 45:55, and even more preferably 20:80 to 40:60. When the weight ratio of component (A) to component (B) ((A) / (B)) satisfies the above range, sufficient water solubility and initial dispersibility can be exhibited while maintaining good tablet formability.

[0133] [1-3. Other ingredients] The powdery composition of the present invention may contain optional components other than the above-mentioned component (A) and component (B) as long as the effects of the present invention are not impaired. When the powdery composition is used as an additive for hydraulic compositions, examples of optional components include known additives for hydraulic compositions, excipients, and lubricants, such as water-soluble polymers, hardening accelerators, thickeners, polymer emulsions, air-entraining agents, cement wetting agents, expansion agents, waterproofing agents, flocculants, drying shrinkage-reducing agents, strength enhancers, antifoaming agents, air-entraining agents, surfactants, etc. These may be used alone or in combination of two or more.

[0134] The water-soluble polymer includes polyalkylene glycol. More specifically, examples thereof include polyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol, polyethylene polybutylene glycol, etc. The content of the water-soluble polymer is preferably 0.01 to 50% by weight based on the weight of component (A).

[0135] Examples of the curing accelerator include soluble calcium salts such as calcium chloride, calcium nitrite, and calcium nitrate; chlorides such as iron chloride and magnesium chloride; thiosulfates; formic acid; and formates such as calcium formate. The curing accelerator may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 50% by weight based on component (A).

[0136] [2. Solid composition] The solid composition of the present invention is a solidified product of the above-mentioned powdery composition. In this specification, the term "solidified product" refers to a processed product obtained by a solidification process. Examples of solidification processes include, but are not limited to, drying and solidification processes, granulation processes (tabletting, extrusion), and various molding processes. Examples of dosage forms of the solid composition include tablets and pellets.

[0137] [3. Additives for hydraulic compositions] The additive for hydraulic compositions of the present invention contains, as an active ingredient, at least one selected from the above-mentioned powdery composition and solid composition. The dosage form of the additive is preferably powdery or solid (e.g., tablet, pellet). When the additive is in powder form, it is preferable that the active ingredient is a powdery composition whose angle of repose and loose bulk density satisfy the above-mentioned conditions. When the additive is in solid form, it is preferable that the active ingredient is a solidified powdery composition whose disintegration angle and particle size distribution satisfy the above-mentioned conditions, and it is even more preferable that the active ingredient is a solidified powdery composition whose disintegration angle and / or difference angle satisfy the above-mentioned conditions.

[0138] In this specification, the powdery additive for hydraulic compositions means an additive for hydraulic compositions that has undergone a drying and solidifying treatment but not a granulation treatment in the manufacturing process, and the solid additive for hydraulic compositions means an additive for hydraulic compositions that has undergone a solidifying treatment such as a drying and solidifying treatment or a granulation treatment in the manufacturing process.

[0139] The water content of the additive for hydraulic compositions is usually 50% by weight or less, preferably 30% by weight or less, and more preferably 10% by weight or less. The water content of the additive for hydraulic compositions can be measured using an infrared moisture meter (manufactured by Kett Electric Laboratory Co., Ltd.). The solid content (%) in the examples below was measured using this instrument.

[0140] The additive for hydraulic compositions may contain components other than the powder composition and the solid composition, for example, other additives for hydraulic compositions such as the agents exemplified in 1-3 above.

[0141] [4. Method for producing powder composition] The present invention provides a method for converting a liquid containing at least component (A) and component (B) into a dry powder. The details of each component are the same as those described in [1. Powdery Composition].

[0142] Drying can be carried out by known methods. Examples include a method in which the polyvalent metal salt is formed by neutralizing the salt with a hydroxide of a divalent metal such as calcium or magnesium and then drying the salt; a method in which the salt is supported on an inorganic powder such as a silica-based fine powder and then dried; a method in which the salt is dried and solidified into a thin film on a support in a drying device (e.g., a drum-type drying device, a disk-type drying device, or a belt-type drying device); and a method in which the salt is dried and solidified using a spray dryer. The moisture content after the drying and solidification process is usually 50% by weight or more, preferably 30% by weight or less, and more preferably 10% by weight or less. The powdered composition obtained after drying and powdering can be used as it is as an additive for a powdered hydraulic composition, or can be further subjected to a solidification treatment to obtain a solidified product which can be used as an additive for a solid hydraulic composition. Examples of the solidification treatment include, but are not limited to, a drying and solidification treatment, a granulation treatment (tabletting, extrusion), and various molding treatments.

[0143] [5. Hydraulic composition] The hydraulic composition of the present invention contains the additive for hydraulic compositions described in 4 above. More specifically, the hydraulic composition is a cement paste, mortar, concrete, plaster, etc. prepared by adding the additive for hydraulic compositions to a hydraulic material such as cement.

[0144] Examples of hydraulic materials include cement, gypsum (gypsum hemihydrate, gypsum dihydrate, etc.), and dolomite. The most common hydraulic material is cement.

[0145] The cement is not particularly limited. Examples include Portland cement (normal, early-strength, ultra-early-strength, moderate-heat, sulfate-resistant, and low-alkali forms of each), various blended cements (blast furnace cement, silica cement, fly ash cement), white Portland cement, alumina cement, ultra-rapid-hardening cement (1-clinker rapid-hardening cement, 2-clinker rapid-hardening cement, magnesium phosphate cement), cement for grouting, oil well cement, low-heat cement (low-heat blast furnace cement, low-heat blast furnace cement mixed with fly ash, high-belite cement), ultra-high-strength cement, cement-based solidifying material, and ecocement (cement produced using one or more of municipal waste incineration ash and sewage sludge incineration ash as raw materials). Blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, limestone powder, and other fine powders, gypsum, etc., may be added to the cement.

[0146] The hydraulic composition may also contain aggregate. The aggregate may be either fine aggregate or coarse aggregate. Examples of the aggregate include sand, gravel, crushed stone, granulated slag, recycled aggregate, silica stone, silica powder, clay, zircon, high alumina, silicon carbide, graphite, chromium, chromium-magnesium, and magnesia refractory aggregate.

[0147] There are no particular limitations on the amount of additive for hydraulic compositions added to a hydraulic composition. For example, when the hydraulic composition is mortar or concrete, the following amounts of additives can be used to uniformly disperse the additive for hydraulic compositions in the cement matrix, suppress thickening of fresh concrete, and prepare a cement composition with good fluidity. The amounts added are expressed as a ratio to the total weight of the hydraulic material (cement).

[0148] The lower limit of the amount of additive for hydraulic compositions (amount of solid content added) is preferably 0.001% by weight or more, more preferably 0.01% by weight or more, and even more preferably 0.1% by weight or more. The upper limit is preferably 30% by weight or less, more preferably 25% by weight or less, and even more preferably 20% by weight or less. That is, the amount is preferably 0.001 to 30% by weight, more preferably 0.01 to 25% by weight, and even more preferably 0.1 to 20% by weight.

[0149] The above hydraulic composition is useful as concrete, for example, ready-mixed concrete, concrete for secondary concrete products (precast concrete), concrete for centrifugal molding, concrete for vibration compaction, steam-cured concrete, lightweight aerated concrete, autoclaved lightweight aerated concrete, and shotcrete. It is also effective as a mortar or concrete that requires high fluidity, such as medium-fluidity concrete (concrete with a slump value in the range of 22 to 25 cm), high-fluidity concrete (concrete with a slump value of 25 cm or more and a slump flow value in the range of 50 to 70 cm), self-compacting concrete, and self-leveling material. [Example]

[0150] The present invention will be described in more detail below with reference to examples. The following examples are provided to suitably explain the present invention and are not intended to limit the present invention. The methods for measuring physical properties and the like are the same as those described above unless otherwise specified. Furthermore, "parts" refers to parts by weight unless otherwise specified.

[0151] [Angle of repose (°)]: This was measured using a powder tester (Powder Tester PT-X (manufactured by Hosokawa Micron Corporation)) with the angle measurement method set to "Peak Operation" using a sieve with a mesh size of 710 μm and a wire diameter of 450 μm, and was used as an index of fluidity. An angle of repose of 50.0° or less indicates excellent powder fluidity and improved workability.

[0152] [Loose bulk density (g / cm 3 )]: Measurement was performed using a powder tester (Powder Tester PT-X (manufactured by Hosokawa Micron Corporation)) using a sieve with a mesh size of 710 μm and a wire diameter of 450 μm. The loose bulk density was 0.40 g / cm 3 If the amount exceeds this range, the diffusibility after the hydraulic composition is introduced deteriorates, and the initial dispersibility deteriorates.

[0153] [Disintegration angle (°)]: Measurement was performed using a powder tester (Powder Tester PT-X (manufactured by Hosokawa Micron Corporation)) with the angle measurement method set to "Peak Operation" using a sieve with a mesh size of 710 μm and a wire diameter of 450 μm. A disintegration angle of 27.0° or more is considered to have excellent tablet suitability and disintegrability.

[0154] [Difference angle (°)]: The difference angle was calculated using the formula (α) below. Difference angle = Angle of repose - Angle of collapse (α) If the difference angle is 19.0° or less, it is determined that the tablet can have excellent tablet suitability and disintegration properties.

[0155] [Particle size distribution (μm)]: 3 g of powder sample was measured under dry conditions using a laser diffraction particle size distribution analyzer (Mastersizer 3000 (Malvern)). From the molecular weight distribution obtained, the horizontal axis is particle size (μm) and the vertical axis is volume (%), and the value at which the cumulative distribution becomes 50% was calculated. If the particle size distribution is 100 μm or more, the cohesive force between particles is improved, and it is determined that the tablet suitability may be improved.

[0156] [Mortar flow (mm)]: The mortar flow of the prepared mortar was measured in accordance with the flow test of "JIS A 1171:2016 (Testing method for polymer cement mortar)".

[0157] [Evaluation of powder fluidity] 1 g of the prepared solid cement dispersant was placed on the inner wall of a stainless steel funnel (inner diameter φ10 mm). Then, while manually vibrating the funnel, it was evaluated whether the solid cement dispersant passed through the funnel. The powder fluidity was judged based on the passage of the solid cement dispersant according to the following criteria. A: The solid cement dispersant passes through the funnel, providing excellent powder fluidity. B: Although the solid cement dispersant adheres to the funnel wall, it passes through the funnel and has slightly better powder fluidity. C: The solid cement dispersant does not pass through the funnel, resulting in poor powder flowability.

[0158] [Evaluation of tablet formability (ease of compaction)]: 10 g of sample was placed in a cylindrical mold with a diameter of 10 cm, dried in a dryer at 50°C for 30 minutes, then removed from the container and visually evaluated. 〇: It is solidified and can be held △: Partially solidified ×: Not solidified and returns to powder when the mold is removed

[0159] [Disintegrability test]: 500 mL of water at 10 to 15°C was placed in a 500 mL measuring cylinder, and the tablet sample prepared in the above tablet formability evaluation was added, and the time it took for the disintegrated sample to fall to the bottom was measured. A disintegration time of 20 seconds or less indicated excellent disintegrability.

[0160] (Production Example 1: Production of Component (A-1)) Wood (radiata pine) was cooked using magnesium sulfite at 140°C for 3 hours under the condition of a solution pH of 2, and the resulting sulfite cooking waste liquor was adjusted to pH 5.0. This was subjected to ultrafiltration using a polysulfone-based ultrafiltration membrane with a molecular weight cutoff of 20,000, and the concentrate was used as the lignin derivative (A-1).

[0161] (Production Example 2: Production of component (A-2)) Wood (radiata pine) was cooked using magnesium sulfite at 140°C for 3 hours under the condition of a solution pH of 2. The resulting sulfite cooking waste liquor was adjusted to pH 12 with 40% NaOH and then subjected to alkaline air oxidation for 30 minutes at 140°C. The insoluble matter was then centrifuged, and the supernatant was used as the lignin derivative (A-2).

[0162] (Production Example 3: Production of component (A-3)) Wood (radiata pine) was digested with calcium sulfite at 140°C for 3 hours under the condition of solution pH 2, and the resulting sulfite digestion waste liquor was adjusted to pH 7.0 to obtain the lignin derivative (A-3).

[0163] (Production Example 4: Preparation of component (B-1)) A glass reactor equipped with a thermometer, stirrer, reflux device, nitrogen inlet tube, and dropping device was charged with 2733 parts of water and 600 parts of an ethylene oxide adduct of methallyl alcohol (average number of moles of ethylene oxide added: 53). The atmosphere in the reactor was replaced with nitrogen while stirring. After heating to 40°C under a nitrogen atmosphere, a monomer aqueous solution containing 126 parts of acrylic acid, 5 parts of 3-mercaptopropionic acid, and 654 parts of water, a mixture of 2 parts of hydrogen peroxide and 244 parts of water, and a mixture of 5 parts of L-ascorbic acid and 245 parts of water were continuously added dropwise to the reactor over 2 hours while maintaining the temperature at 40°C. After the addition, the mixture was allowed to react for another hour while maintaining the temperature, yielding an aqueous copolymer solution. The copolymer in the solution was copolymer (B-1) (weight average molecular weight: 22,000, Mw / Mn: 1.60).

[0164] (Production Example 5: Preparation of component (B-2)) A stainless steel reactor equipped with a thermometer, stirrer, reflux device, nitrogen inlet tube, and dropping device was charged with 7900 kg of water, and the reactor was purged with nitrogen while stirring. After heating to 100 °C under a nitrogen atmosphere, a monomer aqueous solution containing 2503 kg (33 mol%) of methoxypolyethylene glycol methacrylate (MPEG-MA) (average ethylene oxide addition moles: 14), 405 kg (67 mol%) of methacrylic acid (MAA), and 2666 kg of water, along with a stirred mixture of 50 kg of sodium persulfate and 500 kg of water, was continuously added dropwise over two hours to the reactor, which was maintained at 100 °C. The polymerization reaction was carried out for one hour while maintaining the temperature at 100 °C. The mixture was then cooled to 70 °C in an additional device located downstream of the reactor, neutralized to pH 6 with sodium hydroxide, and water was added simultaneously to obtain a 20% copolymer aqueous solution. The copolymer in the liquid was copolymer (B-2) (weight average molecular weight Mw 19,300, Mw / Mn 1.54).

[0165] (Production Example 6: Preparation of component (B-3)) A glass reaction vessel equipped with a thermometer, stirrer, reflux device, nitrogen inlet tube, and dropping device was charged with 254 parts of water, and the atmosphere inside the reaction vessel was replaced with nitrogen while stirring. After heating to 100°C under a nitrogen atmosphere, a monomer aqueous solution containing 35 parts of methacrylic acid, 214 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added: 14), 3 parts of 3-mercaptopropionic acid, and 40 parts of water, and a mixture of 3 parts of ammonium persulfate and 36 parts of water were continuously added dropwise over 2 hours to the reaction vessel maintained at 100°C. The reaction was continued for 1 hour while maintaining the temperature at 100°C. The pH was then adjusted to 7 with a 31% aqueous sodium hydroxide solution, yielding an aqueous copolymer solution. The copolymer in the solution was copolymer (B-3) (weight average molecular weight: 13,000, Mw / Mn: 1.41).

[0166] (Production Example 7: Preparation of component (B-4)) A glass reactor equipped with a thermometer, stirrer, reflux device, nitrogen inlet tube, and dropping device was charged with 654 parts of water and 18 parts of polyethylene glycol monoallyl ether (average number of ethylene oxide added: 10). The atmosphere in the reactor was replaced with nitrogen while stirring. After heating to 80°C under a nitrogen atmosphere, a monomer aqueous solution containing 10 parts of methacrylic acid, 0.1 parts of acrylic acid, 50 parts of methoxypolyethylene glycol methacrylate (average number of ethylene oxide added: 25), 80 parts of 2-hydroxypropyl acrylate, and 142 parts of water, and a mixture of 3 parts of ammonium persulfate and 43 parts of water, were added dropwise over two hours to the reactor, which was maintained at 100°C. After the addition, the mixture was allowed to react for another hour while maintaining the temperature at 100°C, yielding an aqueous copolymer solution. The pH of this solution was adjusted to 4 with a 30% NaOH aqueous solution. The copolymer in the liquid was copolymer (B-4) (weight average molecular weight 24,500, Mw / Mn 2.15).

[0167] (Example 1: Production of additive for powdery hydraulic composition) This powder was prepared by drying component (A-1) and component (B-1) in the formulation shown in Table 1 at 140° C. using a drum dryer. The solid content of the powder was 95%.

[0168] (Example 2: Production of additive for powdery hydraulic composition) This powder was prepared by drying a mixture of component (A-2) and component (B-2) according to the formulation shown in Table 1 in a drum dryer at 140° C. The solid content of the powder was 96%.

[0169] (Examples 3 to 5: Production of additives for powdery hydraulic compositions) The powders were prepared by drying component (A-1) and component (B-2) in a drum dryer at 140°C according to the formulation shown in Table 1. The solid content of the powder in Example 3 was 95%, the solid content of the powder in Example 4 was 97%, and the solid content of the powder in Example 5 was 97%.

[0170] (Example 6: Production of additive for powdery hydraulic composition) The powder was prepared by drying the components (A-1) and (B-3) in the formulation shown in Table 1 at 140° C. using a drum dryer. The solid content of the powder in Example 6 was 95%.

[0171] (Example 7: Production of additive for powdery hydraulic composition) This is a powder obtained by drying component (A-1) and component (B-4) of the formulation shown in Table 1 in a drum dryer at 140° C. The solid content of the powder of Example 7 was 96%.

[0172] (Comparative Example 1: Production of additive for powdery hydraulic composition) This is a powdery product obtained by drying the component (A-1) produced in Production Example 1 using a spray dryer (inlet temperature 300°C, outlet temperature 100°C). The solid content of the powdery product was 94%.

[0173] (Comparative Example 2: Production of additive for liquid hydraulic composition) This is a liquid product prepared using the component (B-3) prepared in Preparation Example 6 as is.

[0174] (Comparative Example 3: Production of additive for liquid hydraulic composition) This is a liquid product prepared using the component (B-4) prepared in Preparation Example 7 as is.

[0175] Details of the additives for hydraulic compositions are shown in Table 1 below.

[0176] [Table 1]

[0177] (Examples 8 to 10: Production of additives for solid hydraulic compositions) The powders were prepared by drying component (A-1) and component (B-3) in a drum dryer at 140°C according to the formulation shown in Table 2. The solid content of the solid product of Example 8 was 97%, the solid content of the solid product of Example 9 was 98%, and the solid content of the solid product of Example 10 was 97%.

[0178] (Example 11: Production of additive for solid hydraulic composition) This powder was prepared by drying a mixture of component (A-1) and component (B-1) according to the formulation shown in Table 2 in a drum dryer at 140° C. The solid content of the powder was 97%.

[0179] (Example 12: Production of additive for solid hydraulic composition) This powder was prepared by drying component (A-1) and component (B-2) in the formulation shown in Table 2 at 140° C. using a drum dryer. The solid content of the powder was 97%.

[0180] (Example 13: Production of additive for solid hydraulic composition) The mixture of component (A-2) and component (B-2) according to the formulation shown in Table 2 was dried in a drum dryer at 140° C. to give a lump. The solid content of the lump was 96%.

[0181] (Example 14: Production of additive for solid hydraulic composition) A mixture of component (A-3) and component (B-2) according to the formulation shown in Table 2 was dried at 140°C in a drum dryer to produce a mass, which was then pulverized for 30 seconds in a sample mill (manufactured by Kyoritsu Riko Co., Ltd., model SK-M2) to produce a pulverized product. The solid content of the pulverized product was 98%.

[0182] (Example 15: Production of additive for solid hydraulic composition) This powder was prepared by drying a mixture of component (A-1) and component (B-3) according to the formulation shown in Table 1 in a drum dryer at 140° C. The solid content of the powder was 97%.

[0183] (Comparative Example 4: Additive for liquid hydraulic composition) This is a liquid product prepared using the component (B-2) prepared in Preparation Example 5 as is.

[0184] Details of the additives for hydraulic compositions are shown in Table 2 below.

[0185] [Table 2]

[0186] Mortar was prepared and a mortar flow test was carried out for each additive for hydraulic compositions shown in Table 1. The conditions for preparing the mortar are shown below.

[0187] At ambient temperature (20°C), cement, water, and sand formulated as shown in Table 3 and additives for hydraulic compositions shown in Tables 4 and 5 were added and mechanically mixed using a mortar mixer at low speed for 60 seconds and high speed for 90 seconds to obtain mortars (hydraulic compositions) of Examples and Comparative Examples. Mortar flow values ​​were measured using these mortars. The test results are shown in Table 4.

[0188] [Table 3]

[0189] Details of the symbols in Table 3 are given below. C: Mix the following three cements in equal amounts: Ordinary Portland cement (manufactured by Ube Mitsubishi Cement Co., Ltd., specific gravity 3.16) Ordinary Portland cement (manufactured by Taiheiyo Cement Corporation, specific gravity 3.16) Ordinary Portland cement (Tokuyama Corporation, specific gravity 3.16) W: Tap water S: Fine aggregate (land sand from Kakegawa, density 2.58)

[0190] [Table 4]

[0191] As can be seen from Table 4, the sintered product contains at least a lignin derivative and a copolymer composed of predetermined structural units, has an angle of repose of 50.0° or less, and a loose bulk density of 0.40 g / cm 3 It can be seen that if the hydroxyl group is less than 100%, the hydroxyl group exhibits powder fluidity equivalent to that of a lignin derivative, and exhibits initial dispersibility and dispersion retention superior to those of a lignin derivative. Furthermore, when Example 6 (using A-1 and B-3) and Comparative Example 2 (using only B-3) are compared, as well as Example 7 (using A-1 and B-4) and Comparative Example 3 (using only B-4), it is found that the powdery hydraulic composition additives of Examples 3 and 4 have greater mortar flow even 30 minutes after mixing than the liquid hydraulic composition additives of Comparative Examples 2 and 3, and therefore have excellent dispersibility. When the same test was carried out on the powdery material of Example 8 (Table 2) with a solid content of 1.20%, the mortar flow immediately after mixing and 30 minutes after mixing was 200 mm and 190 mm, respectively, and the powder fluidity was rated B.

[0192] Mortar was prepared using the additives for hydraulic compositions shown in Table 2, and a mortar flow test was performed. The conditions for preparing the mortar were the same as those described above, except that the additives shown in Table 2 (tablets obtained by the method described in the measurement method for tablet moldability) were used instead of the additives shown in Table 1. The test results are shown in Table 5.

[0193] [Table 5]

[0194] As can be seen from Table 5, all of Examples 8 to 14 had excellent balance between tablet formability and disintegrability. This shows that if a composition contains at least a lignin derivative and a copolymer composed of predetermined structural units, has a disintegration angle of 27.0° or less, and has a particle size distribution of 100 μm or more, it is easy to solidify and the resulting solidified product has good solubility in the hydraulic composition. Furthermore, when Example 10 (using A-1 and B-3) is compared with Comparative Example 2 (using only B-3), and Example 12 (using A-1 and B-2) with Comparative Example 4 (using only B-2), the solid additives for hydraulic compositions of Examples 10 and 12 have mortar flows equal to or greater than those of the liquid additives for hydraulic compositions of Comparative Examples 2 and 4 immediately after mixing and after 30 minutes, indicating that they have dispersibility equal to or greater than that of the liquid additives for hydraulic compositions of Comparative Examples 2 and 4. Furthermore, although Example 13 is a blocky product, it is clear that the mortar flow performance is as excellent as Examples 8 to 12 and 14. Example 15 has good dispersibility and is expected to obtain a good rating (for example, B or higher) in the powder fluidity test.

Claims

1. Component (A): a lignin derivative, and Component (B): A copolymer having at least two types of structural units selected from the group consisting of a structural unit (I) derived from a monomer represented by the following general formula (1), a structural unit (II) derived from a monomer represented by the following general formula (2), and a structural unit (III) derived from a monomer represented by the following general formula (3), and having a weight average molecular weight of 5,000 or more; A powdery composition comprising at least the above, having a particle size distribution of 70 μm or more and an angle of repose of 35.0 to 52.4°. 【Chemistry 1】 (In the general formula (1), R １ ~R ３ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; p represents an integer of 0 to 2; and q represents an integer of 0 to 1. A １ O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. n represents an integer of 1 to 300. R ４ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. 【Chemistry 2】 (In the general formula (2), R ５ ~R ７ are each independently a hydrogen atom, a methyl group, or -(CH ２ ) ｒ COOM ２ represents a group, provided that -(CH ２ ) ｒ COOM ２ When it represents a group, -COOM １ group or other -(CH ２ ) ｒ COOM ２ When an anhydride group is formed, the M １ or M ２ does not exist. １ ~M ２ each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a substituted alkylammonium group; and r represents an integer of 0 to 2. 【Transformation 3】 (In the general formula (3), R ８ ~R １０ R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. １１ represents a hydrocarbon group having 1 to 4 carbon atoms which may contain a heteroatom; and s represents an integer of 0 to 2.

2. The composition of claim 1 , wherein the collapse angle is 27.0° or greater.

3. The composition according to claim 1 or 2, wherein the difference angle represented by the following mathematical formula (α) is 19.0° or less: Difference angle = Angle of repose - Angle of collapse (α)

4. Loose bulk density is 0.40 g / cm ３ The composition according to any one of claims 1 to 3, wherein:

5. 5. The composition according to claim 1, wherein the weight ratio of component (A) to component (B) ((A) / (B)) is from 50:50 to 1:

99.

6. A solid composition which is a solidified product of the composition according to any one of claims 1 to 5.

7. The composition according to claim 6, wherein the solidified product is a solidified product of the composition according to claim 5.

8. An additive for hydraulic compositions, comprising the composition according to any one of claims 1 to 7 as an active ingredient.

9. A hydraulic composition comprising the additive according to claim 8.

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