WO2021015190A1 - Powder composition and use of same - Google Patents

Abstract

The purpose of the present invention is to provide a powder composition which has powder fluidity equivalent to those of conventional powder additives for hydraulic compositions, while having excellent initial dispersibility or being easily solidified and enabling the solidified product to have good solubility and excellent dispersibility in a hydraulic composition, said powder composition being suitable as an additive for hydraulic compositions. The present invention provides a powder composition which contains at least a lignin derivative (component (A)) and a copolymer (component (B)) that is composed of a specific constituent unit, and which satisfies at least one requirement selected from among: the repose angle is 50.0° or less; the loose bulk density is 0.40 g/m³ or less; the collapse angle is 27.0° or more; and the particle size distribution is 100 μm or more. The present invention also provides an additive for hydraulic compositions, said additive using this powder composition.

Description

Powdered composition and its uses

The present invention relates to a powdered composition and its use, and more particularly to a powdered composition, a solid composition, an additive for a hydraulic composition, and a hydraulic composition.

Lignin is a natural polymer substance present in trees and accounts for about 30% of wood. Lignin is abundantly contained in kraft pulp production waste liquid (kraft pulp waste liquid), sulfite pulp production waste liquid (sulfite pulp waste liquid), and the like. From the viewpoint of reducing the environmental load in recent years, lignin tends to attract attention as one of the biomass resources.

Kraft lignin contained in kraft pulp waste liquid and lignin sulfonic acid contained in sulfite pulp waste liquid have different physical properties and are used for various purposes.
In addition, lignin derivatives obtained by sulfomethylating kraft lignin with sulfites and formaldehyde, lignin derivatives obtained by partially desulfonated lignin sulfonic acid or salts of lignin sulfonic acid, and lignin purified products purified by ultrafiltration treatment are lignin. As a system dispersant, it is widely used in a wide range of industrial fields such as dyes, cements, inorganic pigments, organic pigments, gypsum, coal-water slurry, pesticides, and ceramics.

Furthermore, for the purpose of effectively utilizing lignin as a biomass resource, lignin derivatives that can improve the dispersibility of various dispersoids have been proposed regardless of their uses such as cement, dyes, and muddy water for oil field drilling. (See, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2011-240224

Since the solid lignin derivative has good powder properties, it is excellent in workability at the time of transporting or charging the drug.
On the other hand, the conventional lignin derivative as an additive for a hydraulic composition does not have a satisfactory dispersibility effect when added in a small amount. It is necessary to add a large amount of lignin derivative in order to develop initial dispersibility and dispersion retention in the hydraulic composition.
Therefore, it is desired to develop an additive for a powdery hydraulic composition having powder properties equivalent to those of a conventional solid lignin derivative and having excellent initial dispersibility and dispersion retention.

In recent years, tablet molds have begun to emerge as a new product form of additives for hydraulic compositions. Tablet-type additives are superior in transportability and workability as compared with liquid products and powder products, which have been the main product forms of additives for hydraulic compositions.
However, the powder properties of the lignin derivative as an additive for a conventional hydraulic composition are not suitable for tablet moldability, and it is difficult to tablet. Further, even if the tablets could be formed, the solubility of the tablets in the hydraulic composition was poor, and the dispersibility effect was not sufficiently obtained.
Therefore, it is desired to develop an additive for a hydraulic composition that is easy to tablet, has good solubility in the hydraulic composition, and is also excellent in dispersibility.

The first object of the present invention is water having powder characteristics equivalent to those of conventional additives for powdery water-hard composition such as lignin derivatives, and having excellent initial dispersibility and dispersion retention. It is to provide a powdery composition suitable for an additive for a rigid composition.

The second object of the present invention is suitable for producing a solid additive for a hydraulic composition, which is easy to solidify, has good solubility in a hydraulic composition, and is also excellent in dispersibility. Is to provide a powdered composition.

As a result of diligent studies on the above problems, the present inventors have at least containing a lignin derivative and a copolymer composed of a predetermined structural unit, an angle of repose of 50.0 ° or less, and a loose bulk density of 0.4 g / g. We have found that a powdery composition satisfying at least one of m ³ or less, a collapse angle of 27.0 ° or more, and a particle size distribution of 100 μm or more can solve the above problems, and has completed the present invention.

That is, the present inventors provide the following inventions.
[1] Component (A): Lignin derivative, and component (B): Structural unit (I) derived from the monomer represented by the following general formula (1), simple represented by the following general formula (2). A copolymer having at least two structural units selected from the group consisting of a structural unit (II) derived from a polymer and a structural unit (III) derived from a monomer represented by the following general formula (3). Coalescence,
Satisfy at least one selected from an angle of repose of 50.0 ° or less, a loose bulk density of 0.40 g / m ³ or less, a collapse angle of 27.0 ° or more, and a particle size distribution of 100 μm or more. Powdery composition.

(In the general formula (1), R ¹ to R ³ independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. P represents an integer of 0 to 2. q is 0. Represents an integer of 1 to 1. A ¹ O represents an oxyalkylene group having 2 to 18 carbon atoms, which may be the same or different. N represents an integer of 1 to 300. R ⁴ represents a hydrogen atom. Or it represents a hydrocarbon group having 1 to 30 carbon atoms.)

(In the general formula ^{(2), R 5 ~ R} 7 are each independently a hydrogen atom, a methyl group, or _- represents a _(CH ²⁾ r COOM 2 group _{where, -. (CH 2) r} COOM 2 group when referring to, -COOM ¹ group or other _{-. (CH} 2) may be formed r COOM ² groups and anhydride groups when forming anhydride groups, the ^{M 1} or ^{M 2} of these groups present ^No. M ¹ to M ² independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a substituted alkylammonium group. R represents an integer of 0 to 2. )

(In the general formula (3), R ⁸ to R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹¹ contains a hetero atom having 1 to 4 carbon atoms. Represents a hydrocarbon group that may be used. S represents an integer of 0 to 2.)
[2] The composition according to [1], wherein the collapse angle is 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-collapse angle ... (α)
[4] The composition according to any one of [1] to [3], wherein the angle of repose is 50.0 ° or less and the loosening bulk density is 0.40 g / m ³ or less.
[5] The composition according to [4], wherein the weight ratio ((A) / (B)) of the component (A) to the component (B) is 99: 1 to 51:49.
[6] The composition according to any one of [1] to [3], wherein the decay angle is 27.0 ° or more and the particle size distribution is 100 μm or more.
[7] The composition according to [6], wherein the weight ratio ((A) / (B)) of the component (A) to the component (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 a hydraulic composition containing the composition according to any one of [1] to [9] as an active ingredient.
[11] A hydraulic composition containing the additive according to [10].

The following [1-1] to [1-3] are preferable as the powdery additive and its use.
[1-1] Addition for a powdery hydraulic composition containing at least the components (A) and (B), having an angle of repose of 50.0 ° or less, and a loosening bulk density of 0.40 g / m ³ or less. Agent.
[1-2] The powdery hydraulic composition according to [1-1], wherein the weight ratio ((A) / (B)) of the component (A) to the component (B) is 99: 1 to 51:49. Additives for products.
[1-3] A hydraulic composition containing the additive for a powdery hydraulic composition according to [1-1] or [1-2].

The following [2-1] to [2-6] are preferable as the solid additive and its use.
[2-1] For a solid hydraulic composition which is a solidified powder containing at least the components (A) and (B), having a decay angle of 27.0 ° or more and a particle size distribution of 100 μm or more. Additive.
[2-2] The additive for a solid hydraulic composition according to [2-1], which has a decay 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-collapse angle ... (α)
[2-4] Any of [2-1] to [2-3], wherein the weight ratio ((A) / (B)) of the component (A) to the component (B) is 50:50 to 1:99. The additive for a solid hydraulic composition according to item 1.
[2-5] A tablet molded product containing the additive for a solid hydraulic composition according to any one of [2-1] to [2-4].
[2-6] A hydraulic composition containing the additive for a solid hydraulic composition according to any one of [2-1] to [2-4].

According to the present invention, a water-hard composition having powder fluidity equivalent to that of a conventional additive for a powdery water-hard composition such as a lignin derivative, and having excellent initial dispersibility and dispersion retention. A powdery composition suitable for a product additive can be provided.

Further, according to the present invention, it is easy to solidify, and the obtained solidified product has good solubility in a hydraulic composition and is also excellent in dispersibility for producing an additive for a hydraulic composition. A powdery composition suitable for the above can be provided.

Hereinafter, the present invention will be described in detail according to its preferred embodiment.
In addition, in this specification, when it is expressed as "AA-BB", it means AA or more and BB or less. In addition, when it is expressed as "(meth) acrylic", it means acrylic and / or methacrylic.

[1. Powdered composition]
The powdery composition of the present invention contains a component (A): a lignin derivative and a component (B): a copolymer having a predetermined structural unit, has an angle of repose of 50.0 ° or less, and has a loose bulk density of 0. It satisfies at least one of 40 g / m ³ or less, a collapse angle of 27.0 ° or more, and a particle size distribution of 100 μm or more.

[1-1. Physical characteristics]
The angle of repose of the powdered composition is usually 50.0 ° or less, preferably 48.0 ° or less. When the angle of repose is 50.0 ° or less, the powder fluidity 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 test device (Powder Tester PT-X (manufactured by Hosokawa Micron Co., Ltd.)) in a sample prepared with a solid content of 95% or more.

The loose bulk density of the powdered composition is usually 0.40 g / m ³ or less, preferably 0.36 g / m ³ or less. When the loosening bulk density is 0.40 g / m ³ or less, excellent powder fluidity can be obtained. In addition, the diffusibility and initial dispersibility at the time of adding the hydraulic composition are improved.
The lower limit is usually 0.25 g / m ³ or more, but is not particularly limited.
The loose bulk density is a value measured using a powder property test device (Powder Tester PT-X (manufactured by Hosokawa Micron Co., Ltd.)) in a sample having a solid content adjusted to 95% or more.

The decay angle of the powdery composition is usually 27.0 ° or more, preferably 30.0 ° or more. When the disintegration angle is 27.0 ° or more, the powder property is lowered, so that it can have excellent tablet suitability. Further, when a solidified product obtained by solidifying a powdery composition is added to a hydraulic composition, excellent disintegration property can be obtained.
The upper limit of the collapse angle is usually 45.0 ° or less, but is not particularly limited.
The decay angle is a value measured using a powder test device (Powder Tester PT-X (manufactured by Hosokawa Micron Co., Ltd.)) on a sample having a solid content adjusted to 95% or more.

The particle size distribution of the powdery composition is usually 60 μm or more, 65 or more, 70 or more, or 100 μm or more, preferably 105 μm or more, more preferably 107 μm or more, still more preferably 200 μm or more. When the particle size distribution is in the above range, particularly 100 μm or more, the intermolecular interaction is strengthened and the cohesive force between the particles is improved, so that the tablet moldability can be improved.
The upper limit of the particle size distribution is usually 500 μm or less, but is not particularly limited.
Regarding the particle size distribution, the horizontal axis is the particle size (μm) and the vertical axis is from the molecular weight distribution obtained by measuring 3 g of the powder sample with a laser diffraction type particle size distribution measuring device (Mastersizer 3000 (manufactured by Malvern)) under dry conditions. The axis is represented as a volume (%), and the accumulation distribution is a value of 50%.

The difference angle of the powdery composition is preferably 19.0 ° or less. When the difference angle is 19.0 ° or less, the powder property is lowered, so that it can have excellent tablet suitability. Further, when the solidified product is added to the hydraulic composition, excellent disintegration property can be obtained.
The lower limit of the difference angle is usually 5.0 ° or more, but is not particularly limited.
The difference angle is expressed by the following mathematical formula (α).
Difference angle = angle of repose-collapse angle ... (α)
The difference angle is a value based on the difference between the angle of repose and the collapse angle measured using a powder test device (Powder Tester PT-X (manufactured by Hosokawa Micron)) on a sample whose solid content is adjusted to 95% or more. is there.

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

It is difficult to uniformly specify the chemical structure of a lignin derivative using a general formula or the like. The reason is that the lignin constituting the lignin derivative has a very complicated molecular structure.

When the powdery composition of the present invention is used as an additive for a powdery hydraulic composition, the content of the component (A) is 51% by weight or more based on the total amount of the component (A) and the component (B). Preferably, 55% by weight or more is more preferable, and 60% by weight or more is even more preferable. When the content of the component (A) is 51% by weight or more, a powdery substance having good powder fluidity can be obtained in good yield.

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

As the lignin derivative, a prepared one may be used, or a commercially available product may be used. Here, a method for preparing a lignin derivative is exemplified below. However, the lignin derivative is not limited to the one prepared by the following preparation method.

(Method of preparing lignin derivative)
Examples of the method for preparing the lignin derivative include a method for preparing the lignocellulose raw material by treating it with sulfurous acid, and preferably a method for preparing the lignocellulose raw material by treating it with sulfurous acid.

The lignocellulose raw material is not particularly limited as long as it contains lignocellulose in its constituents. For example, pulp raw materials such as wood and non-wood can be mentioned.
Examples of the wood include coniferous wood such as Ezomatsu, Picea glehnii, Sugi, and Hinoki; and broad-leaved wood such as birch and beech. The age of the wood and the collection site do not matter. Therefore, wood collected from trees of different ages or wood collected from different parts of the trees may be used in combination.
Examples of non-wood include bamboo, kenaf, reeds, and rice.
As the lignocellulose raw material, these materials may be used alone or in combination of two or more.

The sulfite treatment is a treatment in which at least one of sulfite and sulfite can be brought into contact with the lignocellulose raw material to obtain an intermediate product. The conditions for the sulfurous acid treatment are not particularly limited as long as the sulfonic acid (salt) group can be introduced into the α carbon atom of the side chain of lignin contained in the lignocellulose raw material.

The sulfurous acid treatment is preferably carried out by a sulfurous acid cooking method. As a result, lignin in the lignocellulose raw material can be sulfonated more quantitatively.
The sulfurous acid cooking method is a method in which a lignocellulose raw material is reacted at a high temperature in at least one solution of sulfite and sulfite (for example, an aqueous solution: a cooking solution). This method has been industrially established and practiced as a method for producing sulfite pulp. Therefore, by performing the sulfurous acid treatment by the sulfurous acid cooking method, economic efficiency and ease of implementation can be improved.

Examples of the sulfite salt include magnesium salt, calcium salt, sodium salt, and ammonium salt when sulfurous acid cooking is performed.

The concentration of sulfurous acid (SO ₂ ) in at least one solution of sulfite and sulfite is not particularly limited, but the ratio of the weight (g) of SO _{2 to} 100 mL of the solution is preferably 1 g / 100 mL or more.

The pH value of the sulfurous acid treatment is not particularly limited, but is preferably 10 or less, and more preferably 5 or less when sulfurous acid cooking is performed. The lower limit of the pH value is preferably 0.1 or more, and more preferably 0.5 or more when sulfurous acid cooking is performed. The pH value during sulfurous acid treatment is preferably 0.1 to 10, and more preferably 0.5 to 5 when sulfurous acid cooking is performed.

The temperature of the sulfurous acid treatment is not particularly limited, but is preferably 170 ° C. or lower. The lower limit is preferably 70 ° C. or higher.

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 in the sulfite treatment can be kept constant. Examples of the compound that supplies the counter cation include MgO, Mg (OH) ₂ , CaO, Ca (OH) ₂ , CaCO ₃ , NH ₃ , NH ₄ OH, NaOH, NaOH, Na HCO ₃ , and Na ₂ CO ₃ . The counter cation is preferably sodium ion, magnesium ion or calcium ion.
The inorganic salt is usually contained in about 3 to 20% in the lignin derivative, and can be measured by a known method.

When at least one solution of sulfite and sulfite is used in the sulfite treatment, in addition to SO ₂ , the above counter cation (salt) and a cooking penetrant (for example, anthraquinone sulfonate, for example, are used in the solution, if necessary. Cyclic ketone compounds such as anthraquinone and tetrahydroanthraquinone) may be included.

The equipment used for the sulfurous acid treatment is not limited, and for example, generally known equipment for producing dissolved pulp can be used.

To separate the intermediate product from at least one solution of sulfite and sulfite, it may be done according to a conventional method. Examples of the separation method include a method for separating the sulfurous acid digestion effluent after the sulfurous acid cooking.

Next, a sulfite-treated product is obtained through a step of washing and dehydrating the intermediate composition. By washing and dehydrating, the components contained in the intermediate composition that cannot be completely removed by the sulfurous acid treatment can be removed.

The washing may be carried out in the same manner as the washing of unbleached sulfite pulp obtained by the sulfite cooking method. The cleaning may be a one-step cleaning or a multi-stage cleaning. By performing multi-step cleaning, cleaning can be sufficiently performed. When performing multi-step washing, dehydration may be performed each time, or may be performed only a part of the times.
Cleaning is usually performed using a washing machine. The washing machine used for washing is not particularly limited. For example, a replacement washing type washing machine and a dilution dehydration washing type washing machine can be mentioned.

Dehydration can be carried out under normal conditions, and may be carried out in the same manner as, for example, dehydration of unbleached sulfite pulp after washing obtained in the sulfite cooking method.
A dehydrator is usually used for dehydration. The dehydrator used for dehydration is not particularly limited. For example, a drum type drawing dehydrator, a rotary press, and a continuous pressing dehydrator can be mentioned.

Then, if necessary, the washed and dehydrated sulfite-treated product is separated and purified to obtain the desired lignin derivative. Examples of the separation and purification include an alkali oxidation treatment step and an ultrafiltration treatment step.

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

Alkaline oxidation treatment may be performed by placing the sulfurous acid-treated product under alkaline conditions. "Keeping under alkaline conditions" usually means putting under an aqueous solution having a pH value of 8 or more, preferably a pH value of 9 or more. The upper limit of the pH value is usually 14.

In the alkali oxidation treatment, an alkaline substance is usually brought into contact with the sulfurous acid-treated product. The alkaline substance is not particularly limited, and examples thereof include calcium hydroxide, magnesium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and ammonia. Of these, sodium hydroxide is preferable.
The alkaline substance may be used alone or in combination of two or more.

As a method of bringing an alkaline substance into contact with the sulfurous acid-treated product, a method of preparing a dispersion or solution (for example, an aqueous dispersion or an aqueous solution) of the sulfite-treated product and adding the alkaline substance to the dispersion or solution, or sulfurous acid An example is a method of adding a solution or dispersion of an alkaline substance (for example, an aqueous dispersion or an aqueous solution) to the treated product.

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

The amount of the alkaline substance in the alkali oxidation treatment is determined based on the solid content weight of the sulfite-treated product, or when preparing an aqueous solution or dispersion in which the alkali-treated extract is dispersed in an aqueous solvent (for example, water). It is preferably 0.5 to 20% by weight, more preferably 1.0 to 15% by weight, based on the weight of the liquid.

The time of the alkali oxidation treatment is not particularly limited, but 0.1 hours or more is preferable, and 0.5 hours or more is more preferable. The upper limit is preferably 10 hours or less, more preferably 6 hours or less.

Prior to the alkali oxidation treatment, the sulfite-treated product may be dissolved, dispersed, and adjusted in concentration (preparation of a solution or dispersion of an aqueous solvent such as water), if necessary. The dispersion treatment can be performed by passing through a disc refiner, adding to a mixer or a disperser, a kneader treatment, or the like. The concentration can be adjusted using, for example, an aqueous solvent such as water.

The ultrafiltration treatment step can be performed using an ultrafiltration membrane (hereinafter, also referred to as “UF membrane”). As the UF membrane, a known UF membrane can be used. For example, a hollow fiber membrane, a spiral membrane, a tubular membrane, and a flat membrane can be mentioned.
A known material for the UF membrane can be used. For example, cellulose acetate, aromatic polyamide, polyvinyl alcohol, polysulfone, polyvinylidene fluoride, polyethylene, polyacrylonitrile, ceramics can be mentioned. The UF membrane may be a commercially available product.

The fractional molecular weight 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. When a UF membrane having a molecular weight cut-off of 5,000 or more is used, it is possible to prevent the black liquor from becoming excessively slow. Further, when a UF membrane having a molecular weight cut-off of 30,000 or less is used, it is possible to prevent lignin from being separated from the black liquor.

The concentration ratio by ultrafiltration using the UF membrane can be set arbitrarily. That is, the ultrafiltration treatment may be stopped when the outflow amount of the concentrated liquid reaches an arbitrary amount.

The temperature of the black liquor during the ultrafiltration treatment is not particularly limited. For example, 20 to 80 ° C. is preferable, and 20 to 70 ° C. is more preferable in consideration of the heat resistant surface of the UF membrane material.
The pH value of the black liquor during the ultrafiltration treatment is preferably 2 to 11.
The solid content concentration (w / w) of the black liquor during the ultrafiltration treatment is preferably 2 to 30%, more preferably 5 to 15%.

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

When the powdered composition of the present invention is used as an additive for a powdered hydraulic composition, the content of the component (B) is 1 to 49% by weight based on the total amount of the component (A) and the component (B). Is preferable, 1 to 45% by weight is more preferable, and 1 to 40% by weight is further preferable. When the content of the component (B) is in such a range, a powdery substance having better water solubility can be obtained after drying.

When the powdered composition of the present invention is used as a raw material for an additive for a solid hydraulic composition, the content of the component (B) is 50 to 50 to the total amount of the component (A) and the component (B). 90% by weight is preferable, and 55 to 90% by weight is more preferable. When the content of the component (B) is in such a range, a solid substance having better water solubility can be obtained after drying.
The details of each structural unit will be described below.

(Constituent unit (I))
The structural unit (I) is a structural unit derived from the monomer represented by the following general formula (1).

In the general formula (1), R ¹ to R ³ independently represent an alkyl group having a hydrogen atom or a carbon atom number of 1 to 3. p represents an integer of 0 to 2. q represents an integer of 0 to 1. A ¹ O represents an oxyalkylene group having 2 to 18 carbon atoms, which may be the same or different. n represents an integer from 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. R ² is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R ³ is preferably a hydrogen atom.

In the general formula (1), A ¹ O represents an oxyalkylene group having 2 to 18 carbon atoms, which may be the same or different. 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 preferable.

The above-mentioned "may be the same or different" means that when a plurality of A ¹ O are contained in the general formula (1) (when n is 2 or more), each A ¹ O is the same oxyalkylene group. It means that they may be different (two or more kinds) oxyalkylene groups from each other. As an embodiment in which a plurality of A ¹ O are contained in the general formula (1), 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 mixed can be mentioned. Be done. More specifically, it is preferable that the oxyethylene group and the oxypropylene group are mixed, or the oxyethylene group and the oxybutylene group are mixed, and the oxyethylene group and the oxypropylene group are mixed. More preferably.
In an embodiment in which different oxyalkylene groups are mixed, the addition of two or more types of oxyalkylene groups may be block-like addition or random addition.

N in the general formula (1) is the average number of moles of the oxyalkylene group 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.

In the general formula (1), R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. R ⁴ 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. When the number of carbon atoms of R ⁴ is in this range, the number of carbon atoms does not become too large, so that the dispersibility is satisfactorily exhibited when it is used as an additive for a hydraulic composition.

As a method for producing a monomer represented by the general formula (1), for example, 1 to 300 alkylene oxides are added to unsaturated alcohols such as allyl alcohol, methallyl alcohol, and 3-methyl-3-buten-1-ol. A method of adding moles can be mentioned. Examples of the monomer produced by this method include (poly) ethylene glycol allyl ether, (poly) ethylene glycol metalyl ether, (poly) ethylene glycol 3-methyl-3-butenyl ether, and (poly) ethylene glycol. (Poly) propylene glycol allyl ether, (poly) ethylene glycol (poly) propylene glycol metallic ether, (poly) ethylene (poly) propylene glycol allyl ether, (poly) ethylene (poly) propylene glycol metallic ether, (poly) ethylene ( Poly) propylene glycol 3-methyl-3-butenyl ether, (poly) ethylene (poly) butylene glycol allyl ether, (poly) ethylene (poly) butylene glycol metallic ether, (poly) ethylene (poly) butylene glycol 3-methyl -3-Butenyl ether, methoxy (poly) ethylene glycol allyl ether, methoxy (poly) ethylene glycol metallic ether, methoxy (poly) ethylene glycol 3-methyl-3-butenyl ether, methoxy (poly) ethylene (poly) propylene Glycolallyl ether, methoxy (poly) ethylene (poly) propylene glycol metallic ether, methoxy (poly) ethylene (poly) propylene glycol 3-methyl-3-butenyl ether, methoxy (poly) ethylene (poly) butylene glycol allyl ether, Examples thereof include methoxy (poly) ethylene (poly) butylene glycol metallic 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) polyethylene 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.

Other methods for producing the monomer represented by the general formula (1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, (poly) ethylene glycol, and (poly) ethylene (poly) propylene. Glycol, (poly) ethylene (poly) butylene glycol, methoxy (poly) ethylene glycol, methoxy (poly) ethylene (poly) propylene glycol, methoxy (poly) ethylene (poly) butylene glycol and other (poly) alkylene glycols. Examples include methods of esterification. Examples of the monomer produced by this method include (poly) ethylene glycol (meth) acrylate, (poly) ethylene (poly) propylene glycol (meth) acrylate, and (poly) ethylene (poly) butylene glycol (meth). (Poly) alkylene glycol (meth) acrylate such as acrylate; methoxy (poly) ethylene glycol (meth) acrylate, methoxy (poly) ethylene (poly) propylene glycol (meth) acrylate, methoxy (poly) ethylene (poly) butylene glycol ( Examples thereof include methoxy (poly) alkylene glycol (meth) acrylate such as (poly) alkylene glycol (meth) acrylate such as meta) acrylate.
Among these, (poly) alkylene glycol (meth) acrylate and methoxy (poly) ethylene glycol (meth) acrylate are preferable, and methoxy (poly) ethylene glycol (meth) acrylate is more preferable.

When the copolymer has a structural unit (I), it may have only one structural unit (I), and has two or more structural units (I) derived from different monomers. You may be.

(Constituent unit (II))
The structural unit (II) is a structural unit derived from the monomer represented by the following general formula (2).

In the general formula ^{(2), R 5 ~ R} 7 are each independently a hydrogen atom, a methyl group, or _- represents a _(CH ²⁾ r COOM 2 group. However, _{- (CH} 2) When referring to r COOM ² group, -COOM ¹ group or other _{- (CH} 2) may be formed r COOM ² groups and anhydride groups. When forming anhydride groups, M ¹ or M ² of those groups is absent. M ¹ to M ² independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a substituted alkylammonium group. r represents an integer of 0 to 2.
R ⁵ is preferably a hydrogen atom. R ⁶ is preferably a hydrogen atom, a methyl group or (CH ₂ ) _r COMM ² . R ⁷ is preferably a hydrogen atom.

M ¹ and M ² are hydrogen atoms, alkali metals, alkaline earth metals, ammonium groups, alkylammonium groups or substituted alkylammonium groups, which may be the same or different. As M ¹ and M ² , hydrogen atoms, alkali metals, or alkaline earth metals are preferable, respectively.

R represents an integer of 0 to 2. r is preferably 0 or 1, more preferably 0.

Examples of the monomer represented by the general formula (2) include unsaturated monocarboxylic acid-based monomers and unsaturated dicarboxylic acid-based monomers. Specific examples of unsaturated monocarboxylic acid-based monomers include acrylic acid, methacrylic acid, crotonic acid, and these monovalent metal salts, ammonium salts, and organic amine salts. Specific examples of the unsaturated dicarboxylic acid include maleic acid, itaconic acid, citraconic acid, fumaric acid and the like, their monovalent metal salts, ammonium salts and organic amine salts and the like, or anhydrides thereof. As the monomer represented by the general formula (2), acrylic acid, methacrylic acid, and maleic acid are preferable.

When the copolymer has a structural unit (II), it may have only one structural unit (II), or has two or more structural units (II) derived from different monomers. You may be.

(Constituent unit (III))
The structural unit (III) is a structural unit derived from the monomer represented by the following general formula (3).

In the general formula (3), R ⁸ to R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹¹ represents a hydrocarbon group which may contain a heteroatom having 1 to 4 carbon atoms. s represents an integer of 0 to 2.
Examples of alkyl groups having 1 to 3 carbon atoms ^are the same as those in ^R 1 ~ R ^3. R ⁸ is preferably a hydrogen atom. R ⁹ is preferably a hydrogen atom. R ¹⁰ is preferably a hydrogen atom.

In the general formula (3), R ¹¹ represents a hydrocarbon group which may contain a heteroatom having 1 to 4 carbon atoms. The number of carbon atoms is preferably 1 to 3, more preferably 2 to 3, and even more preferably 3. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a phosphorus atom, and a silicon atom. Among these, an oxygen atom is preferable. Examples of the hydrocarbon group 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. The number of heteroatoms contained in R ¹¹ may be one or two or more. When two or more heteroatoms are contained, each heteroatom may be the same or different from each other.

R ¹¹ is preferably a hydrocarbon group having 1 to 4 carbon atoms containing a heteroatom, and more preferably a hydrocarbon group having 1 to 4 carbon atoms containing an oxygen atom. Examples of the group include a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, and a glyceryl group. Among these, 2-hydroxyethyl group and 2-hydroxypropyl group are preferable.

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

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

When the copolymer has a structural unit (III), it may have only one structural unit (III), and has two or more structural units (III) derived from different monomers. You may be.

When the copolymer has at least two structural units selected from the group consisting of the above structural units (I) to (III), the coexistence with the component (A) is enhanced, and the component (A) in the cement composition is enhanced. ) Can be dispersed more evenly.

The copolymer may have a structural unit (IV) in addition to the structural units (I) to (III).

(Constituent unit (IV))
The structural unit (IV) is a structural unit derived from a monomer copolymerizable with the monomers represented by the general formulas (1) to (3). The monomers copolymerizable with the monomers represented by the general formulas (1) to (3) are structurally distinguished from the monomers represented by the general formulas (1) to (3). .. The monomer constituting the structural unit (IV) is not particularly limited, and examples thereof include the following monomers.
It should be noted that these monomers can be used alone or in combination of two or more.

Monomer represented by the general formula (IV-1);

Examples of the monomer represented by the general formula (IV-1) include 3 of bisphenols such as 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, and 4,4'-dihydroxydiphenylsulfone. And 3'-position allyl substitutions and the like.

Monomer represented by the general formula (IV-2);

Examples of the monomer represented by the general formula (IV-2) include bisphenols such as 4,4′-dihydroxydiphenylpropane, 4,4′-dihydroxydiphenylmethane, and 4,4′-dihydroxydiphenylsulfone. Examples thereof include 3-position allyl substitution products.

Monomer represented by the general formula (IV-3);

Examples of the monomer represented by the general formula (IV-3) include allylphenol.

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

Half-amides and diamides of the unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms;

A half ester of a (poly) oxyalkylene alkyl ether or (poly) oxyalkylene alkyl amine obtained by adding 1 to 500 mol of an alkylene oxide having 2 to 18 carbon atoms to the alcohol or amine and the unsaturated dicarboxylic acids. , Halfamides, diesters, diamides;

Half-esters and diesters of the unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 moles of these glycols;

Half-amides of maleamic acid and glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 moles of these glycols added;

(Poly) ethylene glycol mono (meth) acrylate and (poly) propylene glycol mono (poly) propylene glycol mono (poly) propylene glycol mono (meth) acrylate in which 1 to 500 mol of alkylene oxide having 2 to 18 carbon atoms is added to unsaturated monocarboxylic acids such as (meth) acrylic acid. Meta) acrylate, (poly) butylene glycol mono (meth) acrylate, etc. (excluding monomers represented by the general formulas (1) to (3));

(Poly) alkylene glycols such as triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate Di (meth) acrylates;

Polyfunctional (meth) acrylates such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane di (meth) acrylate;

(Poly) alkylene glycol dimalates such as triethylene glycol dimalate and polyethylene glycol dimalate;

Vinyl Sulfonate, (Meta) Allyl Sulfonate, 2- (Meta) Acryloxyethyl Sulfonate, 3- (Meta) Acryloxypropyl Sulfonate, 3- (Meta) Acryloxy-2-Hydroxypropyl Sulfonate, 3- (Meta) Acryloxy-2 -Hydroxypropyl sulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxybutyl sulfonate, (meth) acrylamide methyl sulfonic acid, (meth) acrylamide ethyl sulfonic acid, 2- Unsaturated sulfonic acids such as methylpropanesulfonic acid (meth) acrylamide and styrenesulfonic acid, and their monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts;

Amides of unsaturated monocarboxylic acids such as methyl (meth) acrylamide and amines with 1 to 30 carbon atoms;

Vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene;

Alkanediol mono (meth) acrylates such as 1,5-pentanediol mono (meth) acrylate and 1,6-hexanediol mono (meth) acrylate (however, the monomer represented by the general formula (3) is excluded. .);

Dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, 2-chlor-1,3-butadiene;

Unsaturated amides such as (meth) acrylamide, (meth) acrylic alkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide;

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

Unsaturated esters such as vinyl acetate and vinyl propionate;

Unsaturation of (meth) aminoethyl acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, vinylpyridine, etc. Amines (excluding monomers represented by the general formula (3));

Divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate;

Allyls such as (meth) allyl alcohol and glycidyl (meth) allyl ether;

Vinyl ethers such as methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) allyl ether, or allyl ethers (however, a single amount represented by the general formula (1)). Excluding the body.);

Polydimethylsiloxane propylaminomale amidoic acid, polydimethylsiloxane aminopropylene aminomale amidoic acid, polydimethylsiloxane-bis- (propylaminomale amidoic acid), polydimethylsiloxane-bis- (dipropylene aminomale amidoic acid), polydimethyl Siloxane- (1-propyl-3-acrylate), polydimethylsiloxane- (1-propyl-3-methacrylate), polydimethylsiloxane-bis- (1-propyl-3-acrylate), polydimethylsiloxane-bis- (1) A siloxane derivative such as -propyl-3-methacrylate) (excluding the monomer represented by the general formula (3)).

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

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 composed of a combination of two or more types of monomers. It may be a structural unit. Among these, the copolymer is preferably a copolymer which is a combination of the structural unit (I) and the structural unit (II), or a copolymer which is a combination of the structural units (I) to (III).

(Method for preparing copolymer)
Each copolymer can be prepared by copolymerizing predetermined monomers by a known method. Examples of the method include polymerization methods such as polymerization in a solvent and bulk polymerization.

Examples of the solvent used for polymerization in the solvent include water; lower alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; aromatic hydrocarbons such as benzene, toluene and xylene; and fats such as cyclohexane and n-hexane. Group hydrocarbons; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone. From the viewpoint of solubility of the raw material monomer and the obtained copolymer, it is preferable to use at least one solvent of water and a lower alcohol, and it is more preferable to use water.

When the polymerization reaction is carried out in a solvent, each monomer and the polymerization initiator may be continuously added dropwise to the reaction vessel, or a mixture of each monomer and the polymerization initiator may be continuously added dropwise to the reaction vessel. .. Further, the solvent may be charged into the reaction vessel, and the mixture of the monomer and the solvent and the polymerization initiator solution may be continuously added dropwise to the reaction vessel, and a part or all of the monomer may be charged into the reaction vessel to start the polymerization. The agent may be continuously added dropwise.

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

In the polymerization reaction, the molecular weight can be adjusted by using a chain transfer agent, if necessary. Known thiol-based chain transfer agents include, for example, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thioalinic acid, octyl thioglycolate, 2-mercaptoethanesulfonic acid and the like. Compounds; phosphite, hypophosphoric acid, or salts thereof (sodium bisulfite, potassium hypophosphate, etc.), sulfite, hydrogen sulfite, dithionic acid, metabisulfite, or salts thereof (sulfite) Examples thereof include lower oxides of sodium, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, potassium metabisulfite, etc.) or salts thereof.
These chain transfer agents may be used alone or in combination of two or more.

When the polymerization reaction is carried out in an aqueous solvent to obtain a copolymer, the pH at the time of the polymerization reaction is usually strongly acidic due to the influence of a monomer having an unsaturated bond. However, this may be adjusted to an appropriate pH. If it is necessary to adjust the pH during the polymerization reaction, adjust the pH using an acidic substance such as phosphoric acid, sulfuric acid, nitric acid, alkylphosphate, alkylsulfuric acid, alkylsulfonic acid, or (alkyl) benzenesulfonic acid. Good. Among these acidic substances, it is preferable to use phosphoric acid for reasons such as having a pH buffering action. However, in order to eliminate the instability of the ester bond of the ester-based monomer, it is preferable to carry out the polymerization reaction at pH 2 to 7. The alkaline substance that can be used for adjusting the pH is not particularly limited, and alkaline substances such as NaOH and Ca (OH) ₂ are generally used. The pH adjustment may be performed on the monomer before the polymerization reaction or on the copolymer solution after the polymerization reaction. Further, these may be polymerized by adding a part of alkaline substances before the polymerization reaction, and then the pH of the copolymer may be adjusted (for example, adjusted to pH 3 to 7).

The copolymer can be prepared as a liquid. Examples of the liquid solvent include aqueous solvents. Examples of the aqueous solvent include water, alcohols having 1 to 6 carbon atoms (ethyl alcohol, methyl alcohol, ethylene glycol, diethylene glycol, etc.), ketones having 1 to 6 carbon atoms (methylisobutylketone, acetone, etc.), and the like. These aqueous solvents may be used alone or in combination of two or more. Water is preferable 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. The upper limit thereof is preferably 70% by weight or less, more preferably 65% by weight or less.

The 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 of the copolymer. When the copolymer is obtained, the reaction solvent may be removed, concentrated, purified or the like, if necessary. These treatment methods may be conventionally known methods.

The lower limit of the weight average molecular weight (Mw) of the copolymer is preferably 5000 or more, more preferably 7000 or more, and further preferably 10000 or more. By using a copolymer having this weight average molecular weight as the 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 the component (B), the agglutination action of particles in the cement composition can be suppressed, and workability can be improved. The weight average molecular weight is preferably 5000 to 60,000, more preferably 7,000 to 45,000, and even more preferably 10,000 to 30,000.

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 in the range of 1.2 to 3.0, and even more preferably in the range of 1.2 to 2.5.

The weight average molecular weight can be measured by gel permeation chromatography (GPC) by a known method in terms of polyethylene glycol. The measurement conditions for GPC are not particularly limited, and examples thereof include the following conditions. The weight average molecular weight in the latter example is a value measured under this condition.
Measuring device; Tosoh column used: Shodex Volume OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ
Eluent; 0.05 mM sodium nitrate / acetonitrile 8/2 (v / v)
Standard substance: Polyethylene glycol (manufactured by Tosoh or GL Science)
Detector; differential refractometer (manufactured by Tosoh Corporation)
Calibration curve; polyethylene glycol standard

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

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

[1-3. Other ingredients]
The powdery composition of the present invention may contain any component other than the above-mentioned component (A) and component (B) as long as the effect of the present invention is not impaired.
When the powdered composition is used as an additive for a water-hardening composition, optional components include, for example, a water-soluble polymer, a curing accelerator, a thickener, a polymer emulsion, an air entraining agent, a cement wetting agent, and a swelling agent. , Known additives for water-hard composition such as waterproofing agent, coagulant, drying shrinkage reducing agent, strength enhancer, defoaming agent, AE agent, surfactant and the like, excipients and lubricants. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Polyalkylene glycol is a water-soluble polymer. More specifically, polyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol, polyethylene polybutylene glycol and the like can be mentioned. The content of the water-soluble polymer is preferably 0.01 to 50% by weight with respect to the component (A).

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; thiosulfate; 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 with respect to the component (A).

[2. Solid composition]
The solid composition of the present invention is a solidified product of the above-mentioned powdery composition. In the present specification, the solidified product means a processed product obtained by the solidification treatment. Examples of the solidification treatment include a dry solidification treatment, a granulation treatment (locking, extrusion), and various molding treatments, but the solidification treatment is not particularly limited. Examples of the dosage form of the solid composition include tablets and pellets.

[3. Additives for hydraulic compositions]
The additive for a hydraulic composition of the present invention contains at least one selected from the above-mentioned powdery composition and solid composition as an active ingredient. The dosage form of the additive is preferably powder or solid (for example, tablets or pellets). When the dosage form of the additive is in the form of powder, it is preferable to use a powdery composition in which the angle of repose and the loose bulk density satisfy the above conditions as the active ingredient. When the dosage form of the additive is solid, a solid product of a powdery composition in which the collapse angle and particle size distribution satisfy the above conditions is preferable, and further, a powder form in which at least one of the collapse angle and the difference angle satisfies the above conditions. It is more preferable to use the solidified product of the composition as an active ingredient.

In the present specification, the additive for a powdery hydraulic composition means an additive for a hydraulic composition that has undergone a dry solidification treatment but not a granulation treatment in the manufacturing process, and has a solid hydraulic composition. The additive for a material means an additive for a hydraulic composition that has undergone a solidification treatment such as a dry solidification treatment and a granulation treatment in a manufacturing process.

The water content of the additive for the hydraulic composition 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 the hydraulic composition can be measured using an infrared moisture meter (manufactured by Ketsuto Scientific Research Institute Co., Ltd.). The solid content (%) of the examples in the latter stage was measured with this instrument.

The additive for hydraulic composition may contain components other than the powdery composition and the solid composition. For example, other additives for hydraulic composition, each agent exemplified in 1-3 above can be mentioned.

[4. Method for producing powdered composition]
The present invention provides a method for drying and pulverizing a liquid substance containing at least the component (A) and the component (B).
For details of each component, see [1. It is the same as the content described in [Powdered composition].

As a drying method, a known method can be used. For example, a method of neutralizing with a hydroxide of a divalent metal such as calcium or magnesium to obtain a polyvalent metal salt and then drying; a method of supporting and drying on an inorganic powder such as a silica-based fine powder; a drying device ( For example, a method of drying and solidifying in a thin film on a support of a drum type drying device, a disk type drying device or a belt type drying device; a method of drying and solidifying with a spray dryer can be mentioned. The water content after the dry solidification treatment 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 dry powdering can be used as it is as an additive for a powdered hydraulic composition, or a solidified product can be obtained by further solidifying treatment for a solid hydraulic composition. It can be used as an additive. Examples of the solidification treatment include a dry solidification treatment, a granulation treatment (locking, extrusion), and various molding treatments, but the solidification treatment is not particularly limited.

[5. Hydraulic composition]
The hydraulic composition of the present invention contains the additive for hydraulic composition according to 4 above. More specifically, the hydraulic composition is a cement paste, mortar, concrete, plaster or the like prepared by adding an additive for a hydraulic composition to a hydraulic material such as cement.

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

There are no particular restrictions on cement. For example, Portoland cement (normal, early-strength, ultra-fast-strength, moderate heat, sulfate-resistant and each low-alkali form), various mixed cements (blast furnace cement, silica cement, fly ash cement), white Portorand cement, alumina cement, Ultra-fast-hardening cement (1 clinker fast-hardening cement, 2 clinker fast-hardening cement, magnesium phosphate cement), grout cement, oil well cement, low heat-generating cement (low-heat-generating blast furnace cement, fly ash mixed low-heat-generating blast furnace cement, belite High-content cement), ultra-high-strength cement, cement-based solidifying material, eco-cement (cement manufactured from one or more of municipal waste incineration ash and sewage sludge incineration ash) and the like. Fine powder such as blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica sand powder (silica powder), limestone powder, gypsum and the like may be added to the cement.

Further, the hydraulic composition may contain aggregate. The aggregate may be either a fine aggregate or a coarse aggregate. Aggregates include, for example, sand, gravel, crushed stone, granulated slag, recycled aggregate, etc., silica stone, silica sand powder (silica powder), clay, zircon, high alumina, silicon carbide, graphite, chromium. Examples thereof include fire-resistant aggregates such as quality, chromagous, and magnesia.

The amount of the additive for the hydraulic composition added to the hydraulic composition is not particularly limited. For example, when the hydraulic composition is mortar or concrete, the following addition amount uniformly disperses the additive for the hydraulic composition in the cement matrix and suppresses the thickening of fresh concrete. , A cement composition having good fluidity can be prepared. The amount added is a ratio to the total weight of the hydraulic material (cement).

The lower limit of the addition amount (solid content addition amount) of the additive for the hydraulic composition is preferably 0.001% by weight or more, more preferably 0.01% by weight or more, still more preferably 0.1% by weight or more. The upper limit thereof 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, 0.001 to 30% by weight is preferable, 0.01 to 25% by weight is more preferable, and 0.1 to 20% by weight is further preferable.

The above-mentioned water-hardening compositions include, for example, ready-mixed concrete, concrete for secondary concrete products (precast concrete), centrifugal-forming concrete, vibration-compacting concrete, steam-curing concrete, lightweight aerated concrete, Autoclaved Lightweight aerated Concrete, and the like. It is effective as concrete such as sprayed concrete.
In addition, 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-filling concrete, self-leveling material. It is also effective as mortar or concrete that requires high fluidity such as.

Hereinafter, the present invention will be described in detail by way of examples. The following examples are for the purpose of preferably explaining the present invention, and do not limit the present invention. Unless otherwise specified, the method for measuring the physical property value or the like is the measurement method described above. Further, “part” means a part by weight unless otherwise specified.

[Angle of repose (°)]: Measured with a powder test device (Powder Tester PT-X (manufactured by Hosokawa Micron)) using the angle measurement method "Peak Operation" using a sieve with an opening of 710 μm and a wire diameter of 450 μm. It was used as an index of liquidity. When the angle of repose is 50.0 ° or less, the powder fluidity is excellent and the workability is improved.

[Loose bulk density (g / m ³ )]: Measured by a powder property tester (Powder Tester PT-X (manufactured by Hosokawa Micron)) using a sieve having a mesh size of 710 μm and a wire diameter of 450 μm. When the loosening bulk density exceeds 0.40 g / m ³ , the diffusivity after the addition of the hydraulic composition deteriorates, and the initial dispersibility deteriorates.

[Collapse angle (°)]: Measured using a powder test device (Powder Tester PT-X (manufactured by Hosokawa Micron)) with an angle measurement method of "Peak Operation" using a sieve with a mesh size of 710 μm and a wire diameter of 450 μm. .. When the disintegration angle is 27.0 ° or more, it is determined that excellent tablet suitability and disintegration property can be obtained.

[Difference angle (°)]: The difference angle was calculated using the formula expressed by the following mathematical formula (α).
Difference angle = angle of repose-collapse angle ... (α)
When the difference angle is 19.0 ° or less, it is judged that excellent tablet suitability and disintegration property can be obtained.

[Particle size distribution (μm)]: From the molecular weight distribution obtained by measuring 3 g of a powder sample with a laser diffraction type particle size distribution measuring device (Mastersizer 3000 (manufactured by Malvern)) under dry conditions, the horizontal axis is the particle size (μm). , The vertical axis is represented as volume (%), and the value at which the accumulation distribution is 50% is calculated. When the particle size distribution is 100 μm or more, it is determined that the tablet suitability can be improved because the cohesive force between the particles is improved.

[Mortar flow (mm)]: The mortar flow of the prepared mortar was measured according to the flow test of "JIS A 1171: 2016 (test method for polymer cement mortar)".

[Evaluation of powder fluidity]
1 g of the produced solid cement dispersant was placed on the inner wall surface 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 following criteria based on the passing condition of the solid cement dispersant.
A: The solid cement dispersant passes through the funnel and has excellent powder fluidity.
B: Although the solid cement dispersant adheres to the wall surface of the funnel, it passes through the funnel and has slightly excellent powder fluidity.
C: The solid cement dispersant does not pass through the funnel and is inferior in powder fluidity.

[Evaluation of tablet moldability (easiness of solidification)]: A 10 g sample was placed in a cylindrical mold having a diameter of 10 cm, dried in a dryer at 50 ° C. for 30 minutes, removed from the container, and visually evaluated.
〇: Hardened and can be held △: Partially hardened ×: Not hardened and returns to powder when the mold is removed

[Disintegration test]: 500 mL of water at 10 to 15 ° C. was placed in a 500 mL graduated cylinder, the tablet sample prepared by the above tablet moldability evaluation was added, and the time until the disintegrated sample fell to the bottom was measured. If the disintegration time is 20 seconds or less, the disintegration property is excellent.

(Production Example 1: Production of component (A-1))
Wood (radiata pine) was steamed at 140 ° C. for 3 hours under the condition of solution pH 2 using magnesium sulfite, and the obtained sulfurous acid cooking waste liquid was adjusted to pH 5.0. This was subjected to ultrafiltration treatment using a polysulfone-based ultrafiltration membrane having a molecular weight cut off of 20000, and the concentrated solution was used as a lignin derivative (A-1).

(Production Example 2: Production of component (A-2))
Wood (radiata pine) was steamed at 140 ° C. for 3 hours under the condition of solution pH 2 using magnesium sulfite, and the obtained sulfite cooking waste liquid was adjusted to pH 12 with 40% NaOH and then alkaline air-oxidized at 140 ° C. for 30 minutes. .. Then, the insoluble matter was centrifuged, and the supernatant was used as a lignin derivative (A-2).

(Production Example 3: Production of component (A-3))
Wood (radiata pine) was steamed at 140 ° C. for 3 hours under the condition of solution pH 2 using calcium sulfite, and the obtained sulfurous acid cooking waste liquid was adjusted to pH 7.0, and this was used as a lignin derivative (A-3). ..

(Production Example 4: Preparation of component (B-1))
2733 parts of water and 600 parts of ethylene oxide adduct of metallic alcohol (average number of moles of ethylene oxide added: 53) were put into a glass reaction vessel equipped with a thermometer, agitator, a reflux device, a nitrogen introduction tube and a dropping device. Then, the reaction vessel was replaced with nitrogen while stirring. After raising the temperature to 40 ° C. in a nitrogen atmosphere, a mixture of 126 parts of acrylic acid, 5 parts of 3-mercaptopropionic acid, and 654 parts of water, a monomer aqueous solution and 2 parts of hydrogen peroxide, and 244 parts of water and L A mixed solution of 5 parts of ascorbic acid and 245 parts of water was kept at 40 ° C. for 2 hours each and continuously added dropwise to the reaction vessel. After completion of the dropping, the reaction was carried out for another 1 hour while maintaining the temperature to obtain an aqueous solution of the copolymer. The copolymer in the liquid was a copolymer (B-1) (weight average molecular weight 22,000, Mw / Mn 1.60).

(Production Example 5: Preparation of component (B-2))
7900 kg of water was charged into a stainless steel reaction vessel equipped with a thermometer, a stirrer, a recirculation device, a nitrogen introduction tube and a dropping device, and the reaction vessel was replaced with nitrogen under stirring. After raising the temperature to 100 ° C. in a nitrogen atmosphere, 2503 kg (33 mol%) of methoxypolyethylene glycol methacrylate (MPEG-MA) (average number of moles of ethylene oxide added 14), 405 kg (67 mol%) of methacrylic acid (MAA). , And a stirring mixed solution of 50 kg of sodium persulfate and 500 kg of water mixed with 2666 kg of water were continuously added dropwise to a reaction vessel kept at 100 ° C. over 2 hours. The polymerization reaction was carried out for 1 hour while keeping the temperature at 100 ° C. Then, the mixture was cooled to 70 ° C. with an additional device located at the rear stage of the reaction vessel, neutralized to pH 6 with sodium hydroxide, and at the same time hydrated to obtain an aqueous solution of a copolymer having a concentration of 20%. The copolymer in the liquid was a copolymer (B-2) (weight average molecular weight Mw19,300, Mw / Mn1.54).

(Production Example 6: Preparation of component (B-3))
254 parts of water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device, and the inside of the reaction vessel was replaced with nitrogen under stirring. After raising the temperature to 100 ° C. in a nitrogen atmosphere, 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 are mixed. A mixed solution of 3 parts of ammonium persulfate and 36 parts of water was continuously added dropwise to a reaction vessel kept at 100 ° C. for 2 hours each. Further, the reaction was carried out for 1 hour while maintaining the temperature at 100 ° C. Then, the pH was adjusted to 7 with a 31% aqueous sodium hydroxide solution to obtain an aqueous copolymer. The copolymer in the liquid was a copolymer (B-3) (weight average molecular weight 13,000, Mw / Mn1.41).

(Production Example 7: Preparation of component (B-4))
654 parts of water and 18 parts of polyethylene glycol monoallyl ether (average number of added moles of ethylene oxide: 10) were put into a glass reaction vessel equipped with a thermometer, agitator, a reflux device, a nitrogen introduction tube and a dropping device. The reaction vessel was replaced with nitrogen with stirring. After raising the temperature to 80 ° C. in a nitrogen atmosphere, 10 parts of methacrylic acid, 0.1 part of acrylic acid, 50 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added 25), 80 parts of 2-hydroxypropyl acrylate, A monomer aqueous solution containing 142 parts of water and a mixed solution of 3 parts of ammonium persulfate and 43 parts of water were continuously added dropwise to a reaction vessel kept at 100 ° C. for 2 hours each. After completion of the dropping, the reaction was carried out for another 1 hour while maintaining the temperature at 100 ° C. to obtain an aqueous solution of the copolymer. This solution was adjusted to pH 4 with a 30% aqueous NaOH solution. The copolymer in the liquid was a copolymer (B-4) (weight average molecular weight 24,500, Mw / Mn2.15).

(Example 1: Production of additive for powdery hydraulic composition)
It is a powdery substance obtained by drying the component (A-1) and the component (B-1) of the formulations shown in Table 1 at 140 ° C. with a drum dryer. The solid content of the powder was 95%.

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

(Examples 3 to 5: Production of additives for powdery hydraulic composition)
It is a powdery substance obtained by drying the component (A-1) and the component (B-2) of the formulations shown in Table 1 at 140 ° C. with a drum dryer. The solid content of the powdered product of Example 3 was 95%, the solid content of the powdered product of Example 4 was 97%, and the solid content of the powdered product of Example 5 was 97%. It was.

(Example 6: Production of additive for powdery hydraulic composition)
It is a powdery substance obtained by drying the component (A-1) and the component (B-3) of the formulations shown in Table 1 at 140 ° C. with a drum dryer. The solid content of the powdered product of Example 6 was 95%.

(Example 7: Production of additive for powdery hydraulic composition)
It is a powdery substance obtained by drying the component (A-1) and the component (B-4) of the formulations shown in Table 1 at 140 ° C. with a drum dryer. The solid content of the powdered product of Example 7 was 96%.

(Comparative Example 1: Production of Additive for Powdered Hydraulic Composition)
It is a powdery substance obtained by drying the component (A-1) produced in Production Example 1 with a spray dryer (inlet temperature 300 ° C., outlet temperature 100 ° C.). The solid content of the powder was 94%.

(Comparative Example 2: Production of Additive for Liquid Hydraulic Composition)
It is a liquid product using the component (B-3) produced in Production Example 6 as it is.

(Comparative Example 3: Production of Additive for Liquid Hydraulic Composition)
It is a liquid product using the component (B-4) produced in Production Example 7 as it is.

Details of the above additives for hydraulic composition are shown in Table 1 below.

(Examples 8 to 10: Production of additives for solid hydraulic composition)
It is a powdery substance obtained by drying the component (A-1) and the component (B-3) of the formulations shown in Table 2 at 140 ° C. with a drum dryer. The solid content of the solid matter of Example 8 was 97%, the solid content of the solid matter of Example 9 was 98%, and the solid content of the solid matter of Example 10 was 97%. It was.

(Example 11: Production of additive for solid hydraulic composition)
The mixture of the component (A-1) and the component (B-1) of the formulation shown in Table 2 is a powdery product dried at 140 ° C. by a drum dryer. The solid content of the powder was 97%.

(Example 12: Production of additive for solid hydraulic composition)
It is a powdery substance obtained by drying the component (A-1) and the component (B-2) of the formulations shown in Table 2 at 140 ° C. with a drum dryer. The solid content of the powder was 97%.

(Example 13: Production of additive for solid hydraulic composition)
A mixture of the component (A-2) and the component (B-2) of the formulation shown in Table 2 is a mass dried at 140 ° C. with a drum dryer. The solid content of the mass was 96%.

(Example 14: Production of additive for solid hydraulic composition)
A lump of the mixture of the component (A-3) and the component (B-2) of the formulation shown in Table 2 dried at 140 ° C. with a drum dryer was prepared as a sample mill (manufactured by Kyoritsu Riko Co., Ltd., model: It is a crushed product crushed for 30 seconds with SK-M2 type). The solid content of the pulverized product was 98%.

(Example 15: Production of additive for solid hydraulic composition)
The mixture of the component (A-1) and the component (B-3) of the formulation shown in Table 1 is a powdery product dried at 140 ° C. with a drum dryer. The solid content of the powder was 97%.

(Comparative Example 4: Additive for Liquid Hydraulic Composition)
It is a liquid product using the component (B-2) produced in Production Example 5 as it is.

Details of the above additives for hydraulic composition are shown in Table 2 below.

For each additive for hydraulic composition shown in Table 1, mortar was prepared and a mortar flow test was conducted. The conditions for producing mortar are shown below.

At the environmental temperature (20 ° C.), the cement, water, sand and the additives for the hydraulic composition shown in Tables 4 and 5 were added as shown in Table 3, and the mixture was mechanically kneaded with a mortar mixer at low speed for 60 seconds at high speed. The mixture was mixed for 90 seconds to obtain mortars (hydraulic compositions) of Examples and Comparative Examples. Using this mortar, the mortar flow value was measured. The test results are shown in Table 4.

The details of the symbols in Table 3 are shown below.
C: Equivalent mixture of the following three types of cement Ordinary Portland cement (manufactured by Ube-Mitsubishi Cement Co., Ltd., specific gravity 3.16)
Ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd., specific gravity 3.16)
Ordinary Portland cement (manufactured by Tokuyama Corporation, specific gravity 3.16)
W: Tap water S: Fine aggregate (land sand density 2.58 from Kakegawa)

As can be seen from Table 4, if the lignin derivative and the copolymer composed of a predetermined structural unit are contained at least, the angle of repose is 50.0 ° or less, and the loosening bulk density is 0.40 g / m ³ or less. It can be seen that the powder fluidity is equivalent to that of the lignin derivative, and the initial dispersibility and dispersion retention are superior to those of the lignin derivative.
Further, Example 6 (using A-1 and B-3) and Comparative Example 2 (using only B-3), and Example 7 (using A-1 and B-4) and Comparative Example 3 (B-). Comparing (using only 4), the additives for powdered hydraulic composition of Example 3 and Example 4 are 30 after kneading than the additives for liquid hydraulic composition of Comparative Example 2 and Comparative Example 3. Since the mortar flow is large even at the minute, it can be seen that it has excellent dispersibility. When the same test was performed on the powdered material of Example 8 (Table 2) with the solid content added at 1.20%, the mortar flows immediately after kneading and 30 minutes after kneading were 200 mm and 190 mm, respectively, and the powder. Body fluidity was rated B.

For the additives for hydraulic composition shown in Table 2, mortar was prepared and a mortar flow test was conducted. The mortar preparation conditions were the same as those described above, except that the additives shown in Table 2 (tablets obtained by the method described in the method for measuring tablet moldability) were used instead of the additives shown in Table 1. It is the same. The test results are shown in Table 5.

As can be seen from Table 5, all of Examples 8 to 14 were excellent in tablet moldability and disintegration property in a well-balanced manner. From this, if the lignin derivative and the copolymer composed of a predetermined structural unit are contained at least, the decay angle is 27.0 ° or less, and the particle size distribution is 100 μm or more, solidification is easy, and the result is obtained. It can be seen that the solidified product obtained has good solubility in the hydraulic composition.
Further, Example 10 (using A-1 and B-3) and Comparative Example 2 (using only B-3), and Example 12 (using A-1 and B-2) and Comparative Example 4 (B-). Comparing (using only 2), the solid hydraulic composition additives of Examples 10 and 12 were immediately after kneading and 30 with the liquid hydraulic composition additives of Comparative Examples 2 and 4. Since the mortar flow at minutes is the same or larger, it can be seen that the mortar flow has the same or higher dispersibility.
Further, although Example 13 is a lump, it can be seen that the mortar flow performance is as excellent as in Examples 8 to 12 and 14.
Example 15 has good dispersibility, and it is expected that a good evaluation (for example, B or higher) can be obtained in the powder fluidity test.

Claims (11)

1. Component (A): Lignin derivative, and component (B): Structural unit (I) derived from the monomer represented by the following general formula (1), to the monomer represented by the following general formula (2). A copolymer having at least two structural units selected from the group consisting of the derived structural unit (II) and the structural unit (III) derived from the monomer represented by the following general formula (3).
   Satisfy at least one selected from an angle of repose of 50.0 ° or less, a loose bulk density of 0.40 g / m ³ or less, a collapse angle of 27.0 ° or more, and a particle size distribution of 100 μm or more. Powdery composition.
   

   

   (In the general formula (1), R ¹ to R ³ independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. P represents an integer of 0 to 2. q is 0. Represents an integer of 1 to 1. A ¹ O represents an oxyalkylene group having 2 to 18 carbon atoms, which may be the same or different. N represents an integer of 1 to 300. R ⁴ represents a hydrogen atom. Or it represents a hydrocarbon group having 1 to 30 carbon atoms.)
   

   

   (In the general formula ^{(2), R 5 ~ R} 7 are each independently a hydrogen atom, a methyl group, or _- represents a _(CH ²⁾ r COOM 2 group _{where, -. (CH 2) r} COOM 2 group when referring to, -COOM ¹ group or other _{-. (CH} 2) may be formed r COOM ² groups and anhydride groups when forming anhydride groups, the ^{M 1} or ^{M 2} of these groups present ^No. M ¹ to M ² independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a substituted alkylammonium group. R represents an integer of 0 to 2. )
   

   

   (In the general formula (3), R ⁸ to R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹¹ contains a hetero atom having 1 to 4 carbon atoms. Represents a hydrocarbon group that may be used. S represents an integer of 0 to 2.)
2. The composition according to claim 1, wherein the collapse angle is 30.0 ° or more.
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-collapse angle ... (α)
4. The composition according to any one of claims 1 to 3, wherein the angle of repose is 50.0 ° or less and the loosening bulk density is 0.40 g / m ³ or less.
5. The composition according to claim 4, wherein the weight ratio ((A) / (B)) of the component (A) to the component (B) is 99: 1 to 51:49.
6. The composition according to any one of claims 1 to 3, wherein the decay angle is 27.0 ° or more and the particle size distribution is 100 μm or more.
7. The composition according to claim 6, wherein the weight ratio ((A) / (B)) of the component (A) to the component (B) is 50:50 to 1:99.
8. A solid composition which is a solidified product of the composition according to any one of claims 1 to 7.
9. The composition according to claim 8, wherein the solidified product is a solidified product of the composition according to claim 6 or 7.
10. An additive for a hydraulic composition containing the composition according to any one of claims 1 to 9 as an active ingredient.
11. A hydraulic composition containing the additive according to claim 10.