JP2024056323A - Additive for hydraulic composition, manufacturing method thereof and manufacturing method of hydraulic composition - Google Patents

Abstract

[Problem] To provide an additive for hydraulic compositions which maintains air entrainment performance for hydraulic compositions and has improved storage stability. [Solution] An additive for hydraulic compositions which comprises a lignin sulfonic acid compound (A) and water (C), and further contains 0.05 to 10 mass % of an aromatic nonionic surfactant (B). [Selected Figure] None

Description

The present invention relates to an additive for hydraulic compositions, a method for producing the additive, and a method for producing hydraulic compositions. More specifically, the present invention relates to an additive for hydraulic compositions that maintains air entrainment performance in hydraulic compositions and has improved storage stability, a method for producing the additive, and a method for producing hydraulic compositions.

Conventionally, hydraulic compositions such as mortar and concrete should have high fluidity in order to improve workability, and dispersants such as lignin sulfonic acid dispersants, naphthalene sulfonic acid dispersants, melamine sulfonic acid dispersants, and polycarboxylic acid dispersants have been added as additives to impart fluidity to hydraulic compositions.

Each of these dispersants has different characteristics, but lignin sulfonate-based dispersants are known to be able to shorten the setting time (see, for example, Patent Document 1).

Here, lignin is one of the three main components of plant biomass such as wood (the three main components are cellulose, hemicellulose, and lignin), and is the most abundant natural aromatic polymer on earth. The molecular structure of lignin is a complex three-dimensional mesh structure. Lignosulfonic acid is derived from lignin, which is one of the main components that make up plants along with polysaccharides such as cellulose, and is produced, for example, when pulp is produced from plants by the sulfurization process, when lignin is sulfonated as a by-product.

As mentioned above, this lignin sulfonate-based dispersant is derived from plant biomass such as wood, and is produced from wastewater (by-product) produced when producing pulp from plant biomass. Specifically, KP lignin refined from kraft pulp wastewater is sulfomethylated with sulfite and formaldehyde, and lignin sulfonate obtained from sulfite pulp wastewater is known.

Japanese Patent Application Laid-Open No. 63-129049

The AE water-reducing agent in Patent Document 1 is capable of shortening the setting time as described above, but the lignin sulfonate-based dispersing agent has the problem that a large amount of precipitation occurs during storage due to its structure and the fact that it is derived from a plant body as described above.

If a large amount of precipitate is produced, problems arise such as reduced workability in the preparation of the hydraulic composition and poor dispersibility in the hydraulic composition. In order to avoid such problems, the precipitate may be removed before use in the preparation of the hydraulic composition, but this brings about problems such as the time and effort required for removing the precipitate.

In addition, hydraulic compositions such as cement can obtain effects such as improved workability by entraining an appropriate amount of air into them. On the other hand, if the amount of air entrained is too much, it can cause a decrease in the strength of the resulting hardened hydraulic composition. Therefore, when using additives for hydraulic compositions, it is also important not to increase the amount of air entrained.

Therefore, there was a need to develop an additive for hydraulic compositions that would improve storage stability (i.e., would be less likely to cause precipitation during storage) while also having little effect on the amount of entrained air (i.e., would maintain the same amount of entrained air as before).

In view of the above, the object of the present invention is to provide an additive for hydraulic compositions that maintains the air entrainment performance of the hydraulic composition and improves storage stability.

As a result of intensive research aimed at solving the above problems, the inventors have found that the above problems can be solved by employing a specified amount of an aromatic nonionic surfactant (B). According to the present invention, the following additive for hydraulic compositions, a method for producing the additive, and a method for producing a hydraulic composition are provided.

[1] A lignosulfonic acid compound (A) and water (C),
The additive for hydraulic compositions further comprises 0.05 to 10 mass % of an aromatic nonionic surfactant (B).

[2] The additive for hydraulic compositions according to the above [1], wherein the aromatic nonionic surfactant (B) contains at least one selected from the group consisting of aromatic nonionic surfactant (B1) which is a compound represented by the following general formula (1), aromatic nonionic surfactant (B2) which is a compound obtained by condensing a compound represented by the following general formula (2) with a carbonyl compound, and aromatic nonionic surfactant (B3) which is a compound represented by the following general formula (3).

（一般式（１）において、Ｒ^１は、炭素数７～３０のアルキルフェニル基、又は炭素数１４～３０のスチレン化フェニル基である。Ａ^１Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｍは、Ａ^１Ｏの平均付加モル数であり、１～２００の数である。Ｒ^２は、水素原子、又は炭素数１～６の炭化水素基である。）

(In general formula (1), R ¹ is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone, or two or more types may be used). m is the average number of moles of A ¹ O added, and is a number from 1 to 200. R ² is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.)

（一般式（２）において、Ｒ^３は、炭素数７～３０のアルキルフェニル基、又は炭素数１４～３０のスチレン化フェニル基である。Ａ^２Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｎは、Ａ^２Ｏの平均付加モル数であり、１～２００の数である。Ｒ^４は、水素原子、又は炭素数１～６の炭化水素基である。）

(In general formula (2), R ³ is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. A ² O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone, or two or more types may be used). n is the average number of moles of A ² O added, and is a number from 1 to 200. R ⁴ is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.)

（一般式（３）において、Ｒ^５は、ビスフェノールから２個のヒドロキシ基を除いた残基である。Ａ^３Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｐは、Ａ^３Ｏの平均付加モル数であり、１～２００の数である。Ｒ^６は、水素原子、又は炭素数１～６の炭化水素基である。）

(In general formula (3), R ⁵ is a residue obtained by removing two hydroxyl groups from a bisphenol. A ³ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone or two or more types may be used). p is the average number of moles of A ³ O added and is a number from 1 to 200. R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)

[3] In the general formula (1), 30 mol % or more of the total amount of A ¹ O is an oxyethylene group ^, and m is a number from 3 to 150;
In the general formula (2), A ² O is an oxyethylene group that accounts for 30 mol % or more of the total amount of A ² O, and n is a number from 3 to 150;
The additive for hydraulic compositions according to the above [2], wherein A ³ O in the general formula (3) is an oxyethylene group that accounts for 30 mol % or more of the total amount of A ³ O, and p is a number from 3 to 150.

[4] In the general formula (1), R ¹ is a styrenated phenyl group having 14 to 30 carbon atoms and R ² is a hydrogen atom;
In the general formula (2), R ³ is an alkylphenyl group having 10 to 16 carbon atoms or a styrenated phenyl group having 14 to 30 carbon atoms, and R ⁴ is a hydrogen atom;
The additive for hydraulic compositions according to the above [2] or [3], wherein R ⁵ in the general formula (3) is a residue obtained by removing two hydroxyl groups from bisphenol A or bisphenol S, and R ⁶ is a hydrogen atom.

[5] The additive for hydraulic compositions according to [2] or [3], wherein the aromatic nonionic surfactant (B2) has an average degree of condensation of 1.1 to 5.0.

[6] A method for producing an additive for a hydraulic composition, comprising a mixing step of blending a lignin sulfonic acid compound (A), an aromatic nonionic surfactant (B), and water (C) so that the aromatic nonionic surfactant (B) is contained in an amount of 0.05 to 10 mass % of the total.

[7] A method for producing a hydraulic composition, comprising the step of adding an additive for hydraulic compositions according to any one of [1] to [3] above.

The additive for hydraulic compositions of the present invention has the effect of maintaining the air entrainment performance of the hydraulic composition and improving storage stability.

The method for producing an additive for hydraulic compositions of the present invention has the effect of producing an additive for hydraulic compositions of the present invention that maintains the air entrainment performance for the hydraulic composition and has improved storage stability.

The method for producing a hydraulic composition of the present invention includes a step of adding the additive for hydraulic compositions of the present invention, and therefore has the effect of producing a hydraulic composition with good workability since the amount of precipitation derived from the lignin sulfonic acid compound in the additive is small.

The following describes the embodiments of the present invention. However, the present invention is not limited to the following embodiments. Therefore, it should be understood that appropriate modifications and improvements can be made to the following embodiments based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. In the following examples, % means % by mass, and parts means parts by mass, unless otherwise specified.

(1) Additives for hydraulic compositions:
The additive for hydraulic compositions of the present invention contains a lignin sulfonic acid compound (A) and water (C), and further contains 0.05 to 10 mass % of an aromatic nonionic surfactant (B).

By adopting the above-mentioned configuration, this additive for hydraulic compositions maintains the air entrainment performance for hydraulic compositions and improves storage stability.

(1-1) Lignosulfonic acid compound (A):
The lignin sulfonic acid compound (A) functions as a dispersant (lignin sulfonic acid dispersant) for imparting fluidity to hydraulic compositions such as concrete.

This lignin sulfonate compound (A) is derived from lignin, which is one of the main components of plants along with polysaccharides such as cellulose, and is produced, for example, when pulp is produced from plants by the sulfite method (sulfide pulp method), by sulfonating lignin as a by-product. The molecular structure of lignin has a complex three-dimensional mesh structure, and the lignin sulfonate compound (A) obtained by sulfonating lignin also has a complex three-dimensional mesh structure. Thus, lignin sulfonate compound (A) is a by-product derived from natural products (i.e., it contains impurities other than lignin sulfonic acid) and, due to its complex three-dimensional mesh structure, it tends to precipitate a lot during storage.

Specifically, the lignin sulfonic acid compound (A) includes a compound (lignin sulfonic acid) having a skeleton in which the carbon at the α-position of the side chain of the hydroxyphenylpropane structure of lignin is cleaved to introduce a sulfo group. The structure of the skeleton is shown in formula (a).

The lignosulfonic acid compound (A) may include a modified product (modified lignosulfonic acid compound) of a compound having the skeleton represented by the above formula (a). The method (modification method) for obtaining this modified product is not particularly limited, and examples of the method include chemical modification methods such as hydrolysis, alkylation, alkoxylation, sulfonation, sulfonate esterification, sulfomethylation, aminomethylation, and desulfonation, and a method of molecular weight fractionation of the lignosulfonic acid compound by ultrafiltration.

In the present invention, lignin sulfonic acid includes those in the form of salts (i.e., lignin sulfonates). Examples of such salts include monovalent metal salts, divalent metal salts, ammonium salts, and organic ammonium salts.

(1-2) Aromatic nonionic surfactant (B):
The hydraulic composition additive of the present invention is obtained by adding an aromatic nonionic surfactant among surfactants (which often have foaming and defoaming properties) to a lignin sulfonic acid dispersant containing a lignin sulfonic acid compound (A) at a predetermined ratio. By adding an aromatic nonionic surfactant (B) at a predetermined ratio in this way, it is possible to obtain an additive for hydraulic compositions that has improved storage stability while maintaining air entrainment performance for hydraulic compositions. When a surfactant is added to a lignin sulfonic acid dispersant containing a lignin sulfonic acid compound (A), the surfactant may affect the air entrainment performance of the hydraulic composition, and the amount of air entrained in the hydraulic composition may be too large or too small. In this respect, in the present invention, the air entrainment performance is maintained as described above by adding an aromatic nonionic surfactant (B) at a predetermined ratio. Furthermore, it is possible to improve the storage stability of the additive for hydraulic compositions containing a lignin sulfonic acid compound (A).

Here, it is believed that the π-π interaction between the structure derived from phenol contained in the aromatic nonionic surfactant (B) and the structure derived from phenol contained in the lignin sulfonic acid compound (A) contributes efficiently to dispersion stabilization and improves storage stability. This aromatic nonionic surfactant (B) has a small effect on the air entrainment performance of the hydraulic composition (i.e., although surfactants often have foaming and defoaming properties, they are unlikely to contribute to foaming or defoaming), and is therefore effective in solving the problems of the present invention.

The blending ratio of the aromatic nonionic surfactant (B) (ratio to the total amount of the additive for hydraulic compositions) is 0.05 to 10 mass%, preferably 0.2 to 5 mass%. By setting the blending ratio in this range, it is possible to obtain an additive for hydraulic compositions that maintains the air entrainment performance for the hydraulic composition and has improved storage stability.

Specifically, the aromatic nonionic surfactant (B) preferably contains at least one selected from the group consisting of aromatic nonionic surfactant (B1), which is a compound represented by the following general formula (1), aromatic nonionic surfactant (B2), which is a compound obtained by condensing a compound represented by the following general formula (2) with a carbonyl compound, and aromatic nonionic surfactant (B3), which is a compound represented by the following general formula (3). With these, it is possible to obtain an additive for hydraulic compositions that further improves storage stability while further maintaining the air entrainment performance for the hydraulic composition.

（一般式（１）において、Ｒ^１は、炭素数７～３０のアルキルフェニル基、又は炭素数１４～３０のスチレン化フェニル基である。Ａ^１Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｍは、Ａ^１Ｏの平均付加モル数であり、１～２００の数である。Ｒ^２は、水素原子、又は炭素数１～６の炭化水素基である。）

(In general formula (1), R ¹ is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone, or two or more types may be used). m is the average number of moles of A ¹ O added, and is a number from 1 to 200. R ² is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.)

（一般式（２）において、Ｒ^３は、炭素数７～３０のアルキルフェニル基、又は炭素数１４～３０のスチレン化フェニル基である。Ａ^２Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｎは、Ａ^２Ｏの平均付加モル数であり、１～２００の数である。Ｒ^４は、水素原子、又は炭素数１～６の炭化水素基である。）

(In general formula (2), R ³ is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. A ² O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone, or two or more types may be used). n is the average number of moles of A ² O added, and is a number from 1 to 200. R ⁴ is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.)

（一般式（３）において、Ｒ^５は、ビスフェノールから２個のヒドロキシ基を除いた残基である。Ａ^３Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｐは、Ａ^３Ｏの平均付加モル数であり、１～２００の数である。Ｒ^６は、水素原子、又は炭素数１～６の炭化水素基である。）

(In general formula (3), R ⁵ is a residue obtained by removing two hydroxyl groups from a bisphenol. A ³ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone or two or more types may be used). p is the average number of moles of A ³ O added and is a number from 1 to 200. R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)

The aromatic nonionic surfactants (B1) to (B3) are described in detail below.

(1-2a) Aromatic nonionic surfactant (B1):
The aromatic nonionic surfactant (B1) is an aromatic nonionic surfactant which is a compound represented by the following general formula (1).

（一般式（１）において、Ｒ^１は、炭素数７～３０のアルキルフェニル基、又は炭素数１４～３０のスチレン化フェニル基である。Ａ^１Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｍは、Ａ^１Ｏの平均付加モル数であり、１～２００の数である。Ｒ^２は、水素原子、又は炭素数１～６の炭化水素基である。）

(In general formula (1), R ¹ is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone, or two or more types may be used). m is the average number of moles of A ¹ O added, and is a number from 1 to 200. R ² is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.)

By containing the aromatic nonionic surfactant (B1), it is possible to obtain an additive for a hydraulic composition which further maintains the air entraining performance for the hydraulic composition and further improves the storage stability.
R ¹ in general formula (1) is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms, preferably a styrenated phenyl group having 14 to 30 carbon atoms. In this way, it is possible to obtain an additive for hydraulic compositions which further maintains the air entrainment performance for the hydraulic composition and further improves the storage stability.

In general formula (1), A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type alone or two or more types may be used). Preferably, 30 mol % or more of the total amount of A ¹ O is an oxyethylene group, more preferably 45 mol % or more of the total amount is an oxyethylene group, and particularly preferably 80 mol % or more of the total amount is an oxyethylene group. Within such a range, it is possible to obtain an additive for hydraulic compositions which further maintains the air entrainment performance for the hydraulic composition and further improves the storage stability.

In general formula (1), m is the average number of moles of A ¹ O added, and is a number from 1 to 200. And, m is preferably a number from 3 to 150, and more preferably from 5 to 100. Within such a range, it is possible to obtain an additive for a hydraulic composition which further maintains the air entrainment performance for the hydraulic composition and further improves the storage stability.

^R2 in general formula (1) is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom. With such a constitution, it is possible to obtain an additive for hydraulic compositions which further maintains the air entrainment performance for the hydraulic composition and further improves the storage stability.

(1-2b) Aromatic nonionic surfactant (B2):
The additive for hydraulic composition of the present invention contains an aromatic nonionic surfactant (B2) obtained by condensing a compound represented by the following general formula (2) with a carbonyl compound. That is, the aromatic nonionic surfactant (B2) is a compound having a structure formed by condensing a compound represented by the general formula (2) with a carbonyl compound.

In general formula (2), R ³ is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. A ² O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone, or two or more types may be used). n is the average number of moles of A ² O added, and is a number from 1 to 200. R ⁴ is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.

By including the aromatic nonionic surfactant (B2), it is possible to obtain an additive for hydraulic compositions that further maintains the air entrainment performance for the hydraulic composition while further improving storage stability.

The aromatic nonionic surfactant (B2) preferably has an average condensation degree of 1.1 to 5.0, more preferably 1.2 to 4.0. By setting the average condensation degree within such a range, it is possible to obtain an additive for hydraulic compositions that further improves storage stability while further maintaining the air entrainment performance for the hydraulic composition.

The average condensation degree of the aromatic nonionic surfactant (B2) can be calculated by measuring the following mass average molecular weights by gel permeation chromatography (GPC) and using the formula: Average condensation degree = mass average molecular weight of aromatic nonionic surfactant (B2) ÷ (mass average molecular weight of the compound represented by general formula (2) + mass molecular weight of the carbonyl compound).

The aromatic nonionic surfactant (B2) is a condensation reaction product obtained by condensing a compound represented by general formula (2) with a carbonyl compound, and is a compound containing a structure derived from the compound represented by general formula (2) and a structure derived from a carbonyl compound. In other words, the aromatic nonionic surfactant (B2) in the present invention can also be said to be a compound containing a structure derived from an alkylphenyl compound or a structure derived from a styrenated phenyl compound, an alkylene oxide structure, and a structure derived from a carbonyl compound.

(1-2b-1) Compound represented by formula (2):
R ³ in general formula (2) is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms, preferably an alkylphenyl group having 10 to 16 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms, and more preferably a styrenated phenyl group having 14 to 30 carbon atoms. In this way, it is possible to obtain an additive for hydraulic compositions which further maintains the air entrainment performance for the hydraulic composition, while further improving the storage stability.

In general formula (2), A ² O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type alone or two or more types may be used). Preferably, 30 mol % or more of the total amount of A ² O is an oxyethylene group, more preferably 45 mol % or more of the total amount is an oxyethylene group, and particularly preferably 80 mol % or more of the total amount is an oxyethylene group. Within such a range, it is possible to obtain an additive for hydraulic compositions which further maintains the air entrainment performance for the hydraulic composition while further improving the storage stability.

In general formula (2), n is the average number of moles of A ² O added, and is a number from 1 to 200. And, n is preferably a number from 3 to 150, and more preferably from 5 to 100. When it is in such a range, it is possible to obtain an additive for a hydraulic composition which further maintains the air entrainment performance for the hydraulic composition and further improves the storage stability.

^R4 in general formula (2) is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom. With such a constitution, it is possible to obtain an additive for hydraulic compositions which further maintains the air entrainment performance for the hydraulic composition and further improves the storage stability.

(1-2b-2) Carbonyl compounds:
The carbonyl compound is not particularly limited, and examples thereof include formaldehyde, acetaldehyde, benzaldehyde, acetone, and methyl ethyl ketone. Among these, formaldehyde is preferred. When formaldehyde is used, the condensation reaction product of the aromatic nonionic activator (B2) is produced well (in high yield), and the storage stability of the lignin sulfonic acid compound (A) is improved.

(1-2c) Aromatic nonionic surfactants (B3):
The aromatic nonionic surfactant (B3) is an aromatic nonionic surfactant which is a compound represented by the following general formula (3).

（一般式（３）において、Ｒ^５は、ビスフェノールから２個のヒドロキシ基を除いた残基である。Ａ^３Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｐは、Ａ^３Ｏの平均付加モル数であり、１～２００の数である。Ｒ^６は、水素原子、又は炭素数１～６の炭化水素基である。）

(In general formula (3), R ⁵ is a residue obtained by removing two hydroxyl groups from a bisphenol. A ³ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone or two or more types may be used). p is the average number of moles of A ³ O added and is a number from 1 to 200. R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)

By containing the aromatic nonionic surfactant (B3), it is possible to obtain an additive for a hydraulic composition which further maintains the air entraining performance for the hydraulic composition and further improves the storage stability.
^R5 in general formula (3) is a residue obtained by removing two hydroxy groups from bisphenol, and is preferably a residue obtained by removing two hydroxy groups from bisphenol A or bisphenol S. In this way, it is possible to obtain an additive for hydraulic compositions which further maintains the air entrainment performance for the hydraulic composition and further improves the storage stability.

In general formula (3), A ³ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type alone or two or more types may be used). Preferably, 30 mol % or more of the total amount of A ³ O is an oxyethylene group, more preferably 45 mol % or more of the total amount is an oxyethylene group, and particularly preferably 80 mol % or more of the total amount is an oxyethylene group. Within such a range, it is possible to obtain an additive for hydraulic compositions which further maintains the air entrainment performance for the hydraulic composition while further improving the storage stability.

In general formula (3), p is the average number of moles of A ³ O added, and is a number from 1 to 200. And, p is preferably a number from 3 to 150, and more preferably from 5 to 100. When it is in such a range, it is possible to obtain an additive for a hydraulic composition which further maintains the air entrainment performance for the hydraulic composition and further improves the storage stability.

^R6 in general formula (3) is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom. With such a constitution, it is possible to obtain an additive for hydraulic compositions which further maintains the air entrainment performance for the hydraulic composition and further improves the storage stability.

Two or more of the aromatic nonionic surfactants (B1) to (B3) may be used simultaneously, and there are no particular restrictions on the content ratio of each, as long as the total of these (i.e., the ratio of the aromatic nonionic surfactant (B)) is in the range of 0.05 to 10 mass%. For example, the content ratio of each of the aromatic nonionic surfactants (B1) to (B3) can be 0.05 to 10 mass%.

(1-3) Water (C):
The water (C) is not particularly limited, and any water that is used in conventional additives for hydraulic compositions, such as lignin sulfonic acid-based dispersants, can be appropriately used.

There are no particular limitations on the mixing ratio of water (C) (ratio to the total amount of additives for hydraulic compositions), but it can be, for example, 10 to 99 mass %.

Conventional lignin sulfonate-based dispersants, which are aqueous liquids containing water like the additive for hydraulic compositions of the present invention, have low stability and are prone to large amounts of precipitation, but in the present invention, by including the above-mentioned aromatic nonionic surfactant (B) in a specified ratio, it is possible to suppress the occurrence of precipitation and improve storage stability.

(1-4) Other components:
The additive for hydraulic compositions of the present invention may further contain other components in addition to the lignin sulfonic acid compound (A), the aromatic nonionic surfactant (B), and water (C).

Other components include, for example, sodium gluconate, polycarboxylic acid dispersants, sugars, rust inhibitors, shrinkage reducing agents, defoamers, air entraining agents, preservatives, thickeners, etc.

The content ratio of the other components can be, for example, 0 to 50% by mass, preferably 0 to 25% by mass, and more preferably 0 to 15% by mass, relative to the total amount of the additive for hydraulic compositions.

(2) Manufacturing method of additive for hydraulic composition:
The method for producing an additive for hydraulic composition of the present invention includes a mixing step of blending a lignin sulfonic acid compound (A), an aromatic nonionic surfactant (B), and water (C) so that the aromatic nonionic surfactant (B) is contained in an amount of 0.05 to 10 mass % of the total.

According to this method for producing an additive for hydraulic compositions, it is possible to produce the additive for hydraulic compositions of the present invention that maintains the air entrainment performance for the hydraulic composition and has improved storage stability.

(2-1) Mixing step:
In this step, the lignin sulfonic acid compound (A), the aromatic nonionic surfactant (B), and the water (C) may all be mixed together, or a portion of each may be mixed first and then the remaining portion may be mixed in. For example, the lignin sulfonic acid compound (A) and the water (C) may be mixed, and then the aromatic nonionic surfactant (B) may be mixed.

The proportion of the aromatic nonionic surfactant (B) in the entire hydraulic composition additive is 0.05 to 10 mass%, preferably 0.2 to 5 mass%. By setting the proportion in this manner, it is possible to obtain an additive for hydraulic compositions that maintains the air entrainment performance for the hydraulic composition and has improved storage stability.

There are no particular limitations on the method for mixing the components, and any conventional method can be used as appropriate.

For example, the mixing temperature can be between 5 and 80°C.

(3) Hydraulic composition:
The additive for hydraulic compositions of the present invention is used by being added to hydraulic compositions.

This hydraulic composition, like conventionally known hydraulic compositions, contains a binder (hydraulic binder), water, fine aggregate, coarse aggregate, etc.

The content ratio of the additive for hydraulic compositions of the present invention in this hydraulic composition is not particularly limited and can be set appropriately. For example, the content ratio of the additive for hydraulic compositions of the present invention can be 0.01 to 5.0 parts by mass per 100 parts by mass of the binder.

Examples of binders include various types of Portland cement, such as ordinary Portland cement, moderate heat Portland cement, low heat Portland cement, high early strength Portland cement, and sulfate-resistant Portland cement, as well as various types of cement, such as blast furnace cement, fly ash cement, and silica fume cement.

Furthermore, the binder may be used in combination with various admixtures such as fly ash, ground granulated blast furnace slag, ground limestone, stone powder, silica fume, and expansive agents.

Fine aggregates include, for example, river sand, mountain sand, land sand, sea sand, silica sand, crushed sand, various types of slag fine aggregates, etc., but may also contain fine particles such as clay.

Examples of coarse aggregates include river gravel, mountain gravel, land gravel, crushed stone, various types of slag coarse aggregate, lightweight aggregate, etc.

The hydraulic composition may further contain other components as appropriate, provided that the effect is not impaired. Examples of such other components include setting retarders made of sugars, oxycarboxylates, etc., various fluidizing agents, air entraining agents made of anionic surfactants, antifoaming agents made of oxyalkylene compounds, hardening accelerators made of alkanolamines, shrinkage reducers made of polyoxyalkylene alkyl ethers, thickeners made of cellulose ether compounds, quick-setting agents made of calcium sulfonates, preservatives made of isothiazolinone compounds, and rust inhibitors made of nitrites.

The content ratio of other components can be, for example, 0 to 5 parts by weight per 100 parts by weight of binder.

The ratio of water to binder in the hydraulic composition (water/binder ratio) can be any ratio known in the art, but can be, for example, 20 to 70% by mass, and preferably 30 to 65% by mass.

(4) Method for producing hydraulic composition:
The method for producing a hydraulic composition of the present invention includes a step of adding the additive for hydraulic composition of the present invention (additive adding step). According to this method for producing a hydraulic composition, by including a step of adding the additive for hydraulic composition of the present invention, the amount of precipitate derived from the lignosulfonic acid compound in the additive is small, so that the hydraulic composition can be produced with good workability. That is, when a large amount of precipitate derived from the lignosulfonic acid compound is present in the additive for hydraulic composition containing the lignosulfonic acid compound, it is troublesome to stir the additive for hydraulic composition before use to dissolve the precipitate. In addition, if the additive for hydraulic composition is used while the precipitate remains, it is considered that the precipitate will eventually be removed. These operations tend to be troublesome in producing a hydraulic composition. On the other hand, if the amount of precipitate derived from the lignosulfonic acid compound is small, the above-mentioned operations can be omitted, and the hydraulic composition can be produced with good workability.

In the additive addition step, the method of adding the additive for the hydraulic composition of the present invention is not particularly limited, and any conventionally known method can be appropriately adopted.

In addition, when producing the hydraulic composition, the binders and other components constituting the hydraulic composition can be appropriately mixed by conventionally known methods. Examples of components such as binders include those mentioned above.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

First, the lignosulfonic acid compounds (A) (LS-1 to LS-3) used in the examples and comparative examples are shown in Table 1 below.

Next, the aromatic nonionic surfactants (B) (B1-1 to B1-11, B2-1 to B2-4, B3-1 to B3-3, BR-1, BR-2) used in the examples and comparative examples are shown in Tables 2 to 4 below.

In Tables 2 and 3, the number of moles of oxyethylene (EO) added and the number of moles of oxypropylene (PO) added are calculated values assuming that each main component of styrenated phenol (specifically, monostyrenated phenol (mono form), distyrenated phenol (di form), and tristyrenated phenol (tri form)) is 100. Note that each main component of the mono-, di-, and tri-forms is a group shown in the "R ¹ " column in Table 2 and the "R ³ " column in Table 3. For example, in the case of B1-1 in Table 2, it is "monostyrenated phenol" which becomes a monostyrenated phenyl group.

In Table 2, "BR-1" is a commercially available lauryl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) to which 6 moles of ethylene oxide have been added. "BR-2" is Mighty 150 (manufactured by Kao Corporation) used as is. In Table 2, "EO" stands for ethylene oxide and "PO" stands for propylene oxide. In Table 2, "random" in the "addition form" column means that the alkylene oxide was added randomly.

(Synthesis Example 1)
Aromatic nonionic surfactants (B1-1) to (B1-3), (B1-5), and (B1-6)
309.8 g of monostyrenated phenol "SP-F" (manufactured by Sankosha) and 4.2 g of 48% aqueous potassium hydroxide solution were added to an autoclave, and the inside of the autoclave was fully replaced with nitrogen, and then dehydration was performed under reduced pressure at 120°C while stirring. Thereafter, 688.2 g of ethylene oxide was injected at a gauge pressure of 0.4 MPa at this temperature and reacted, and the reaction was completed by aging at the above temperature for 1 hour. Thereafter, neutralization filtration was performed using Kyoward 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) to obtain an aromatic nonionic surfactant (B1-1).

In addition, "SP-F (product name) manufactured by Sankosha" is a compound that is composed of 65 mol % or more of mono-styrenated phenol (i.e., monostyrenated phenol), 32 mol % or less of di-styrenated phenol (i.e., distyrenated phenol), and 1 mol % or less of tri-styrenated phenol (i.e., tristyrenated phenol).

(Synthesis Examples 2, 3, 5, and 6)
Aromatic nonionic surfactants (B1-2), (B1-3), (B1-5), (B1-6)
Aromatic nonionic surfactants (B1-2), (B1-3), (B1-5), and (B1-6) were obtained in the same manner as in Synthesis Example 1, except that "TSP" (manufactured by Sankosha) was used in the case of a tristyrenated phenyl group, and "SP-24" (manufactured by Sankosha) was used in the case of a distyrenated phenyl group.

"Sankosha's SP-24 (product name)" is a compound that is 0 mol% mono (i.e., monostyrenated phenol), 60 mol% or more di (i.e., distyrenated phenol), and 40 mol% or less tri (i.e., tristyrenated phenol). "Sankosha's TSP (product name)" is a compound that is 0 mol% mono (i.e., monostyrenated phenol), 30 mol% or less di (i.e., distyrenated phenol), and 65 mol% or more tri (i.e., tristyrenated phenol).

(Synthesis Example 4)
Aromatic nonionic surfactants (B1-4)
131.2 g of tristyrenated phenol "TSP" (manufactured by Sankosha) and 3.2 g of 48% aqueous potassium hydroxide solution were added to the autoclave, and the inside of the autoclave was fully replaced with nitrogen, and then dehydration was performed under reduced pressure at 120°C while stirring. Then, at this temperature, 1179.9 g of ethylene oxide and 187.4 g of propylene oxide were simultaneously injected at a gauge pressure of 0.4 MPa to react, and the reaction was completed by aging at the above temperature for 1 hour. Then, neutralization filtration was performed using Kyoward 600 to obtain an aromatic nonionic surfactant (B1-4).

(Synthesis Examples 7, 8, 10, and 11)
Aromatic nonionic surfactants (B1-7), (B1-8), (B1-10), (B1-11)
Aromatic nonionic surfactants (B1-7), (B1-8), (B1-10), and (B1-11) were obtained in the same manner as in Synthesis Example 4, except that "paraoctylphenol (POP)" (manufactured by Maruzen Petrochemical Co., Ltd.) was used in the case of an octylphenyl group, and "SP-24" (manufactured by Sankosha Co., Ltd.) was used in the case of a distyrenated phenyl group.

(Synthesis Example 9)
Aromatic nonionic surfactants (B1-9)
In the same manner as in Synthesis Example 1, a reaction product was obtained by adding 105 moles of ethylene oxide to tristyrenated phenol. Thereafter, 503.2 g of the reaction product was again charged into the autoclave, and 6.2 g of potassium hydroxide was added, followed by dehydration under reduced pressure at 120°C. Thereafter, 5.1 g of methyl chloride was reacted at 90°C. After completion of the reaction, the mixture was aged at this temperature for 4 hours to complete the reaction. Thereafter, neutralization and desalting treatment were performed to obtain an aromatic nonionic surfactant (B1-9).

In Table 3, "EO" stands for ethylene oxide, and "PO" stands for propylene oxide. In Table 3, "block" in "addition form" means that alkylene oxide is block-added.

(Synthesis Example 10)
Aromatic nonionic surfactants (B2-1)
406.6 g of tristyrenated phenol "TSP" (manufactured by Sankosha), 3.8 g of p-toluenesulfonic acid monohydrate, and 18.0 g of paraformaldehyde were added to the autoclave, and condensed at 110 ° C. for 3 hours while refluxing. Then, 7.8 g of 48% potassium hydroxide aqueous solution was added, and the inside of the autoclave was sufficiently replaced with nitrogen, and then dehydration was performed under reduced pressure at 120 ° C. while stirring. Then, at this temperature, 2068.0 g of ethylene oxide was injected at a gauge pressure of 0.4 MPa to react, and the reaction was completed by aging at the above temperature for 1 hour. Then, neutralization filtration was performed using Kyoward 600 to obtain an aromatic nonionic surfactant (B2-1).

(Synthesis Example 11)
Aromatic nonionic surfactants (B2-2)
302.4 g of distyrenated phenol "SP-24" (manufactured by Sankosha), 1.9 g of methanesulfonic acid, and 30.0 g of paraformaldehyde were added to the autoclave, and condensed at 110 ° C. for 3 hours while refluxing. Then, 4.1 g of 48% potassium hydroxide aqueous solution was added, and the inside of the autoclave was sufficiently replaced with nitrogen, and then dehydration was performed under reduced pressure at 120 ° C. while stirring. Then, at this temperature, 352 g of ethylene oxide and 58.1 g of propylene oxide were simultaneously injected at a gauge pressure of 0.4 MPa and reacted, and the reaction was completed by aging at the above temperature for 1 hour. Then, neutralization filtration was performed using Kyoward 600 to obtain an aromatic nonionic surfactant (B2-2).

(Synthesis Example 12)
Aromatic nonionic surfactants (B2-3)
206.3 g of octylphenol "paraoctylphenol (POP)" (manufactured by Maruzen Petrochemical Co., Ltd.), 3.8 g of p-toluenesulfonic acid monohydrate, and 206.3 g of paraformaldehyde were added to the autoclave, and condensed at 110 ° C. for 5 hours while refluxing. Then, 6.8 g of 48% potassium hydroxide aqueous solution was added, and the inside of the autoclave was sufficiently replaced with nitrogen, and then dehydration was performed under reduced pressure at 120 ° C. while stirring. Then, at this temperature, 1760 g of ethylene oxide was injected at a gauge pressure of 0.4 MPa and reacted, and then 116.0 g of propylene oxide was injected at a gauge pressure of 0.4 MPa and reacted, and the reaction was completed by aging at the above temperature for 1 hour. Then, neutralization filtration was performed using Kyoward 600 to obtain an aromatic nonionic surfactant (B2-3).

(Synthesis Example 13)
Aromatic nonionic surfactants (B2-4)
An aromatic nonionic surfactant (B2-4) was obtained in the same manner as in Synthesis Example 11, except that tristyrenated phenol "TSP" (manufactured by Sankosha) was used instead of distyrenated phenol "SP-24" (manufactured by Sankosha).

In Table 4, "EO" stands for ethylene oxide, and "PO" stands for propylene oxide. In Table 4, "block" in "addition form" means that alkylene oxide is block-added.

(Synthesis Example 14)
Aromatic nonionic surfactants (B3-1)
318.9 g of "Newpol BPE-60" (manufactured by Sanyo Chemical Industries, Ltd.), which is an adduct of 6 moles of ethylene oxide added to all hydroxyl groups of 2,2-bis(4-hydroxyphenyl)propane, and 3.0 g of potassium hydroxide were added to an autoclave, and the inside of the autoclave was thoroughly replaced with nitrogen, and then dehydration was carried out under reduced pressure at 120°C while stirring. Then, 2681.1 g of ethylene oxide was injected at a gauge pressure of 0.4 MPa at this temperature to react, and the reaction was completed by aging for 1 hour at the above temperature. Then, the mixture was neutralized and filtered using Kyoward 600 to obtain an aromatic nonionic surfactant (B3-1).

(Synthesis Example 15)
Aromatic nonionic surfactants (B3-2)
250.3 g of commercially available bis(4-hydroxyphenyl)sulfone (Tokyo Chemical Industry Co., Ltd.) and 8.0 g of potassium tert-butoxide were added to the autoclave, and the inside of the autoclave was sufficiently replaced with nitrogen, and then the temperature was raised to 120 ° C. while stirring. Then, 176 g of ethylene oxide was charged at this temperature, and the reaction was started. After confirming that the pressure had decreased, 5544.0 g of ethylene oxide was further injected into the reaction system at a gauge pressure of 0.4 MPa and reacted, and then 580.0 g of propylene oxide was further injected at a gauge pressure of 0.4 MPa and reacted, and the reaction was completed by aging at the above temperature for 1 hour. Then, the mixture was neutralized and filtered using Kyoward 600 to obtain an aromatic nonionic surfactant (B3-2).

(Synthesis Example 16)
Aromatic nonionic surfactants (B3-3)
An aromatic nonionic surfactant (B3-3) was obtained in the same manner as in Synthesis Example 14, except that the amount of ethylene oxide was changed so as to satisfy Table 4.

(Average Condensation Degree)
For the prepared aromatic nonionic surfactants (B2) ((B2-1) to (B2-3)), the weight average molecular weight was measured by gel permeation chromatography (GPC) under the measurement conditions shown below, and the average condensation degree was calculated using the following formula.

<Method of calculating average condensation degree>
Average condensation degree = mass average molecular weight of aromatic nonionic surfactant (B2) ÷ (mass average molecular weight of compound represented by general formula (2) + mass molecular weight of carbonyl compound)

<Conditions for measuring weight average molecular weight>
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK gel Super H4000 + TSK gel Super H3000 + TSK gel Super H2000 (manufactured by Tosoh Corporation)
Detector: differential refractometer (RI)
Eluent: tetrahydrofuran Flow rate: 0.5 mL/min Column temperature: 40° C.
Sample concentration: Eluent solution with a sample concentration of 0.5% by mass Standard material: Polystyrene (manufactured by Tosoh Corporation)

Next, the polycarboxylic acid-based dispersants (referred to as "PCE" in Table 5) (PC-1 to PC-4) used when preparing the hydraulic composition using formulation (2) are shown in Table 5 below.

In Table 5, "M-1" to "M-4", "AAA", "MA", and "HEA" are specifically shown below.
M-1: α-methacrylic-ω-methoxy-poly(9 mol)oxyethylene M-2: α-(3-methyl-3-butenyl)-ω-hydroxy-poly(50 mol)oxyethylene M-3: α-methallyl-ω-hydroxy-poly(113 mol)oxyethylene M-4: α-methacrylic-ω-methoxy-poly(45 mol)oxyethylene MAA: methacrylic acid AA: acrylic acid MA: methyl acrylate HEA: hydroxyethyl acrylate

(Synthesis Example 17)
1. Method for Producing Polycarboxylic Acid Dispersant (Reaction Mixture (PC-1)) 148.1 g of α-methacryl-ω-methoxy-poly(9 mol)oxyethylene, 30.0 g of methacrylic acid, 9.4 g of methyl acrylate, 4.1 g of 3-mercaptopropionic acid and 181.0 g of ion-exchanged water were charged into a reaction vessel having an internal volume of 1 L, and after uniformly dissolving with stirring, the atmosphere was replaced with nitrogen. The temperature of the reaction system was kept at 60° C. in a hot water bath, and 31.4 g of a 6.2% aqueous solution of sodium persulfate was dropped to start polymerization, and the polymerization reaction was continued for 6 hours to complete the polymerization. After cooling, a 30% aqueous solution of sodium hydroxide was added to obtain a pH of 7, and the concentration was further adjusted to 40% with ion-exchanged water to obtain a polycarboxylic acid dispersant (PC-1) which is the reaction mixture (PC-1). When this reaction mixture (PC-1) was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 18,600.

(Synthesis Example 18)
Method for producing polycarboxylic acid-based dispersant (reaction mixture (PC-2)) 102.6 g of ion-exchanged water and 180.6 g of α-(3-methyl-3-butenyl)-ω-hydroxy-poly(n = 50)oxyethylene were charged into a reaction vessel with an internal volume of 1 L, and after uniform dissolution with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was set to 65 ° C. in a hot water bath. Thereafter, a solution obtained by diluting 15.7 g of acrylic acid with 76.5 g of ion-exchanged water was dropped over 3 hours, and at the same time, 9.8 g of 3.5% hydrogen peroxide solution was dropped into the reaction system over 3 hours, and at the same time, a solution obtained by diluting 0.8 g of 3-mercaptopropionic acid and 0.8 g of L-ascorbic acid with 6.3 g of ion-exchanged water was dropped into the reaction system over 4 hours. The temperature of the reaction system was further maintained at 65 ° C. and aged for 1 hour. The pH was adjusted to 5 using a 30% aqueous sodium hydroxide solution, and the concentration was adjusted to 40% using ion-exchanged water to obtain a polycarboxylic acid dispersant (PC-2) which is a reaction mixture (PC-2). When this reaction mixture (PC-2) was analyzed by gel permeation chromatography (GPC), it was found to have a mass average molecular weight of 32,000.

(Synthesis Example 19)
Method for producing polycarboxylic acid-based dispersant (reaction mixture (PC-3)) 151.0 g of ion-exchanged water and 177.0 g of α-methallyl-ω-hydroxy-oxypropylene poly(113 mol)oxyethylene were added to a reaction vessel with an internal volume of 1 L, and after uniform dissolution with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was set to 70 ° C. in a hot water bath. A solution obtained by diluting 11.8 g of acrylic acid and 7.9 g of hydroxyethyl acrylate with 31.5 g of ion-exchanged water was dropped over 3 hours, and at the same time, 8.9 g of 3.5% hydrogen peroxide solution was dropped into the reaction system over 3 hours, and at the same time, a solution obtained by diluting 1.0 g of 3-mercaptopropionic acid and 0.8 g of L-ascorbic acid with 7.1 g of ion-exchanged water was dropped into the reaction system over 4 hours. The temperature of the reaction system was further maintained at 60 ° C. and aged for 0.5 hours. The pH was adjusted to 7 using a 30% aqueous sodium hydroxide solution, and the concentration was adjusted to 40% using ion-exchanged water to obtain a polycarboxylic acid dispersant (PC-3), which is a reaction mixture (PC-3). When this reaction mixture (PC-3) was analyzed by gel permeation chromatography (GPC), it was found to have a mass average molecular weight of 39,000.

(Synthesis Example 20)
Manufacturing method of polycarboxylic acid dispersant (reaction mixture (PC-4)) 103.4g of ion-exchanged water was added to a reaction vessel with an internal volume of 1L, the atmosphere was replaced with nitrogen while stirring, and the temperature of the reaction system was set to 65 ° C. in a warm water bath. An aqueous solution of 311.7g of α-methacrylic-ω-methoxy-poly (45 mol) oxyethylene, 77.9g of methacrylic acid, and 2.7g of 3-mercaptopropionic acid dissolved in 342.5g of ion-exchanged water was dropped over 3 hours, and at the same time, 24.3g of 7% hydrogen peroxide solution was dropped over 4 hours. The temperature of the reaction system was further maintained at 65 ° C. and aged for 1 hour. A 30% aqueous sodium hydroxide solution was added to adjust the pH to 5.6, and the concentration was adjusted to 40% with ion-exchanged water to obtain a polycarboxylic acid dispersant (PC-4) which is a reaction mixture (PC-4). When this reaction mixture (PC-4) was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 35,000.

(Method of measuring mass average molecular weight)
The method for measuring the mass average molecular weight of the reaction mixtures (PC-1) to (PC-4) was as follows.
Apparatus: Shodex GPC-101 (manufactured by Showa Denko Co., Ltd.)
Column: OHpak SB-806M HQ + SB-806M HQ (Showa Denko)
Detector: differential refractometer (RI)
Eluent: 50 mM sodium nitrate aqueous solution Flow rate: 0.7 mL/min Column temperature: 40° C.
Sample concentration: Eluent solution with a sample concentration of 0.5% by mass Standard substances: polyethylene glycol, polyethylene oxide (Agilent)

(Examples 1 to 30, Comparative Examples 1 to 7)
(1) Preparation of additive for hydraulic composition:
The lignin sulfonic acid compound (A), the aromatic nonionic surfactant (B) produced as described above, and water (C) were mixed in the types and ratios shown in Tables 6 and 7 below to prepare additives for hydraulic compositions (L-1 to L-30, R-1 to R-7). Tap water (Gamagori City tap water) was used as the mixing water other than the water contained in each component, and in Examples 6 and 27, sodium gluconate (reagent: manufactured by Kishida Chemical Co., Ltd.) (denoted as "GS" in Table 6) was mixed as another component. In Examples 24 to 30 and Comparative Example 7, polycarboxylic acid dispersants (PC-1) to (PC-4) shown in Table 7 were further mixed in a predetermined mixing ratio as another component.

In Tables 6 and 7, for example, in Example 10, "B1-1/B2-1" for aromatic nonionic surfactant (B) means that aromatic nonionic surfactants (B1-1) and (B2-1) are blended together. In Example 10, "1.0/0.5" in "% by mass" means that 1.0% by mass of aromatic nonionic surfactant (B1-1) and 0.5% by mass of aromatic nonionic surfactant (B2-1) are blended together.

(2) Preparation of hydraulic composition (concrete composition):
Next, hydraulic compositions were prepared using the prepared additives for hydraulic compositions (L-1 to L-30, R-1 to R-7) as follows. Table 8 shows the mix conditions of the hydraulic compositions (concrete compositions), mix (1) and mix (2).

First, the mix (1) will be described below. In a thermostatic room at 20°C and humidity of 80%, under the mix conditions shown in Table 8, a 55-L pan-type forced mixer was used to mix the concrete with a hydraulic binder consisting of ordinary Portland cement (an equal mixture of Pacific Cement Corporation, Ube Mitsubishi Cement Corporation, and Sumitomo Osaka Cement Co., Ltd., density = 3.16 g/cm ³ ), fine aggregate (Oigawa River water system sand and land sand, density = 2.58 g/cm ³ ) and coarse aggregate (Okazaki crushed stone, density = 2.68 g/cm ^{3 ).} ), and further, 0.4 mass% of additives for hydraulic compositions (L-1 to L-23, R-1 to R-6) based on cement, 0.2 mass% of 10 mass% aqueous solution of sodium gluconate (Kishida Chemical Co., Ltd.) based on cement, and 0.002 mass% of commercially available air-enhancing agent "AE-300 (Takemoto Yushi Co., Ltd.)" based on cement were measured as a part of mixing water (tap water), and the mixture was put into a mixer and mixed for 60 seconds to prepare 30 L of hydraulic compositions (concrete compositions) of Examples 1 to 23 and Comparative Examples 1 to 6. At this time, the target air content was set to 4.5% and the target slump was set to 15.5 cm.

The temperature of each material was adjusted before preparation so that the temperature of the mixed concrete composition was within the range of 20±2°C. The temperature of the mixed concrete composition was measured in accordance with JIS-A1156 (2014).

Next, the mix (2) will be described below. In a thermostatic room at 20°C and humidity of 80%, under the mix conditions shown in Table 8, a pan-type forced mixer with a nominal capacity of 55 L was used to mix the concrete with a hydraulic binder consisting of ordinary Portland cement (an equal mixture of Pacific Cement Corporation, Ube Mitsubishi Cement Corporation, and Sumitomo Osaka Cement Co., Ltd., density = 3.16 g/cm ³ ), fine aggregate (Oigawa River water system sand and land sand, density = 2.58 g/cm ³ ) and coarse aggregate (Okazaki crushed stone, density = 2.68 g/cm ^{3 )} . ), and further, 1.0% by mass of additives for hydraulic compositions (L-24 to L-30, R-7) based on cement, 0.002% by mass of a commercially available air entrainer AE-300 (Takemoto Yushi Co., Ltd.) based on cement, and 0.0005% by mass of a commercially available antifoaming agent AFK-2 (Takemoto Yushi Co., Ltd.) based on cement were weighed as part of the mixing water (tap water), charged into a mixer, and mixed for 90 seconds. In this way, 30 L of hydraulic compositions (concrete compositions) of Examples 24 to 30 and Comparative Example 7 were prepared. At this time, the target air content was set to 4.5% and the target slump was set to 18.0 cm.

As with Mixture (1), the temperature of each material was adjusted before preparation so that the temperature of the mixed concrete composition was within the range of 20±2°C. The temperature of the mixed concrete composition was measured in accordance with JIS-A1156 (2014).

Next, various evaluations were performed on the prepared hydraulic compositions (stability, slump, air content (%), difference from standard for air content, AE property, and overall evaluation). The evaluation results are shown in Tables 6 and 7.

The evaluation methods and evaluation criteria for each of the prepared hydraulic compositions are shown below.

(Stability)
Each of the prepared hydraulic composition additives (L-1 to L-30, R-1 to R-7) was added to a 100 mL Fine oil settling tube (graduated) (Tokyo Glass Instruments Co., Ltd.) up to the 100 mL mark. At this time, each hydraulic composition additive was thoroughly shaken just before being added to the settling tube. Thereafter, the settling tube containing each hydraulic composition additive was left to stand in a room at 25°C, and the degree of settling of the precipitate (amount of sediment) was checked after 14 days.

The stability was evaluated based on the following criteria.
S: When the amount of sediment is 0.5 mL or less A: When the amount of sediment is more than 0.5 mL and less than 1.0 mL B: When the amount of sediment is more than 1.0 mL and less than 2.0 mL C: When the amount of sediment is more than 2.0 mL

(slump)
The hydraulic composition (concrete composition) immediately after mixing was measured in accordance with JIS-A1101 (2020).

(Air volume (%))
The hydraulic composition (concrete composition) immediately after mixing was measured in accordance with JIS-A1128 (2019).

(Difference from standard for air volume)
The difference in air volume from the standard air volume (air volume in Comparative Example 1) was calculated according to the formula: "difference in air volume from standard (%) = air volume in each Example and Comparative Example (%) - standard air volume (%)".

(AE)
In the case of formulation (1) which did not contain an aromatic nonionic surfactant (polycarboxylic acid-based dispersants (PC-1) to (PC-4)), the air amount of Comparative Example 1 was used as the standard, and in the case of formulation (2), the air amount of Comparative Example 7 was used as the standard. Evaluation was performed according to the following evaluation criteria.
S: When the difference between the air volume and the standard is within ±1.0% A: When the difference between the air volume and the standard is more than ±1.0% and within ±1.5% B: When the difference between the air volume and the standard is more than ±1.5% and within ±2.0% C: When the difference between the air volume and the standard is more than ±2.0%

(comprehensive evaluation)
Based on the evaluation results of stability and AE, a comprehensive evaluation was made according to the following criteria.
S: When both stability and AE are S A: When stability and AE are S and A, or A and S B: When either stability or AE is B C: When either stability or AE is C

(result)
As shown in Tables 6 and 7, the hydraulic composition additives of Examples 1 to 30 have better AE properties than the hydraulic composition additives of Comparative Examples 1 to 7, so that they maintain the air entraining performance for the hydraulic composition, and the stability evaluation is good, so that it was confirmed that an additive for a hydraulic composition with improved storage stability can be obtained.

The hydraulic composition additive of the present invention can be used as an additive for hydraulic compositions such as concrete and mortar. The manufacturing method of the hydraulic composition additive of the present invention can be adopted as a method for manufacturing the hydraulic composition additive of the present invention. The hydraulic composition of the present invention can be used to form a hydraulic composition hardened body such as a concrete hardened body or a mortar hardened body.

The present invention relates to an additive for hydraulic compositions and a method for producing hydraulic compositions. More specifically, the present invention relates to an additive for hydraulic compositions that maintains air entrainment performance for hydraulic compositions and has improved storage stability , and a method for producing hydraulic compositions.

Conventionally, hydraulic compositions such as mortar and concrete should have high fluidity in order to improve workability, and dispersants such as lignin sulfonic acid dispersants, naphthalene sulfonic acid dispersants, melamine sulfonic acid dispersants, and polycarboxylic acid dispersants have been added as additives to impart fluidity to hydraulic compositions.

Each of these dispersants has different characteristics, but lignin sulfonate-based dispersants are known to be able to shorten the setting time (see, for example, Patent Document 1).

Here, lignin is one of the three main components of plant biomass such as wood (the three main components are cellulose, hemicellulose, and lignin), and is the most abundant natural aromatic polymer on earth. The molecular structure of lignin is a complex three-dimensional mesh structure. Lignosulfonic acid is derived from lignin, which is one of the main components that make up plants along with polysaccharides such as cellulose, and is produced, for example, when pulp is produced from plants by the sulfurization process, when lignin is sulfonated as a by-product.

As mentioned above, this lignin sulfonate-based dispersant is derived from plant biomass such as wood, and is produced from wastewater (by-product) produced when producing pulp from plant biomass. Specifically, KP lignin refined from kraft pulp wastewater is sulfomethylated with sulfite and formaldehyde, and lignin sulfonate obtained from sulfite pulp wastewater is known.

Japanese Patent Application Laid-Open No. 63-129049

The AE water-reducing agent in Patent Document 1 is capable of shortening the setting time as described above, but the lignin sulfonate-based dispersing agent has the problem that a large amount of precipitation occurs during storage due to its structure and the fact that it is derived from a plant body as described above.

If a large amount of precipitate is produced, problems arise such as reduced workability in the preparation of the hydraulic composition and poor dispersibility in the hydraulic composition. In order to avoid such problems, the precipitate may be removed before use in the preparation of the hydraulic composition, but this brings about problems such as the time and effort required for removing the precipitate.

In addition, hydraulic compositions such as cement can obtain effects such as improved workability by entraining an appropriate amount of air into them. On the other hand, if the amount of air entrained is too much, it can cause a decrease in the strength of the resulting hardened hydraulic composition. Therefore, when using additives for hydraulic compositions, it is also important not to increase the amount of air entrained.

Therefore, there was a need to develop an additive for hydraulic compositions that would improve storage stability (i.e., would be less likely to cause precipitation during storage) while also having little effect on the amount of entrained air (i.e., would maintain the same amount of entrained air as before).

In view of the above, the object of the present invention is to provide an additive for hydraulic compositions that maintains the air entrainment performance of the hydraulic composition and improves storage stability.

As a result of intensive research aimed at solving the above problems, the present inventors have found that the above problems can be solved by adopting a predetermined amount of an aromatic nonionic surfactant (B). According to the present invention, the following additive for hydraulic compositions and a method for producing a hydraulic composition are provided.

（一般式（１）において、Ｒ ^１ は、炭素数７～３０のアルキルフェニル基、又は炭素数１４～３０のスチレン化フェニル基である。Ａ ^１ Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｍは、Ａ ^１ Ｏの平均付加モル数であり、１～２００の数である。Ｒ ^２ は、水素原子、又は炭素数１～６の炭化水素基である。）

（一般式（２）において、Ｒ ^３ は、炭素数７～３０のアルキルフェニル基、又は炭素数１４～３０のスチレン化フェニル基である。Ａ ^２ Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｎは、Ａ ^２ Ｏの平均付加モル数であり、１～２００の数である。Ｒ ^４ は、水素原子、又は炭素数１～６の炭化水素基である。）

（一般式（３）において、Ｒ ^５ は、ビスフェノールから２個のヒドロキシ基を除いた残基である。Ａ ^３ Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｐは、Ａ ^３ Ｏの平均付加モル数であり、１～２００の数である。Ｒ ^６ は、水素原子、又は炭素数１～６の炭化水素基である。） [1] A composition comprising a lignosulfonic acid compound (A) and water (C),
Further, it contains 0.05 to 10 mass % of an aromatic nonionic surfactant (B),
The aromatic nonionic surfactant (B) contains at least one selected from the group consisting of an aromatic nonionic surfactant (B1) which is a compound represented by the following general formula (1), an aromatic nonionic surfactant (B2) which is a compound obtained by condensing a compound represented by the following general formula (2) with a carbonyl compound, and an aromatic nonionic surfactant (B3) which is a compound represented by the following general formula (3),
In the general formula (1), R ¹ is a styrenated phenyl group having 14 to 30 carbon atoms and R ² is a hydrogen atom;
In the general formula (2), R ³ is an alkylphenyl group having 10 to 16 carbon atoms or a styrenated phenyl group having 14 to 30 carbon atoms, and R ⁴ is a hydrogen atom;
A hydraulic composition additive, characterized in that R ⁵ in the general formula (3) is a residue obtained by removing two hydroxy groups from bisphenol A or bisphenol S, and R ⁶ is a hydrogen atom.

(In general formula (1), R ¹ is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone, or two or more types may be used). m is the average number of moles of A ¹ O added, and is a number from 1 to 200. R ² is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.)

(In general formula (2), R ³ is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. A ² O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone, or two or more types may be used). n is the average number of moles of A ² O added, and is a number from 1 to 200. R ⁴ is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.)

(In general formula (3), R ⁵ is a residue obtained by removing two hydroxyl groups from a bisphenol. A ³ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone or two or more types may be used). p is the average number of moles of A ³ O added and is a number from 1 to 200. R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)

[2] A lignosulfonic acid compound (A) and water (C),
Further, it contains 0.05 to 10 mass % of an aromatic nonionic surfactant (B),
The aromatic nonionic surfactant (B) contains at least one selected from the group consisting of an aromatic nonionic surfactant (B1) which is a compound represented by the following general formula (1), an aromatic nonionic surfactant (B2) which is a compound obtained by condensing a compound represented by the following general formula (2) with a carbonyl compound, and an aromatic nonionic surfactant (B3) which is a compound represented by the following general formula (3),
The additive for hydraulic compositions, wherein the aromatic nonionic surfactant (B2) has an average degree of condensation of 1.1 to 5.0.

（一般式（１）において、Ｒ^１は、炭素数７～３０のアルキルフェニル基、又は炭素数１４～３０のスチレン化フェニル基である。Ａ^１Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｍは、Ａ^１Ｏの平均付加モル数であり、１～２００の数である。Ｒ^２は、水素原子、又は炭素数１～６の炭化水素基である。）

(In general formula (1), R ¹ is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone, or two or more types may be used). m is the average number of moles of A ¹ O added, and is a number from 1 to 200. R ² is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.)

（一般式（２）において、Ｒ^３は、炭素数７～３０のアルキルフェニル基、又は炭素数１４～３０のスチレン化フェニル基である。Ａ^２Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｎは、Ａ^２Ｏの平均付加モル数であり、１～２００の数である。Ｒ^４は、水素原子、又は炭素数１～６の炭化水素基である。）

(In general formula (2), R ³ is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. A ² O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone, or two or more types may be used). n is the average number of moles of A ² O added, and is a number from 1 to 200. R ⁴ is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.)

（一般式（３）において、Ｒ^５は、ビスフェノールから２個のヒドロキシ基を除いた残基である。Ａ^３Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｐは、Ａ^３Ｏの平均付加モル数であり、１～２００の数である。Ｒ^６は、水素原子、又は炭素数１～６の炭化水素基である。）

(In general formula (3), R ⁵ is a residue obtained by removing two hydroxyl groups from a bisphenol. A ³ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone or two or more types may be used). p is the average number of moles of A ³ O added and is a number from 1 to 200. R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)

[3] In the general formula (1), 30 mol % or more of the total amount of A ¹ O is an oxyethylene group ^, and m is a number from 3 to 150;
In the general formula (2), A ² O is an oxyethylene group that accounts for 30 mol % or more of the total amount of A ² O, and n is a number from 3 to 150;
The additive for hydraulic compositions according to the above [1] or [2], wherein A ³ O in the general formula (3) is an oxyethylene group that accounts for 30 mol % or more of the total amount of A ³ O, and p is a number from 3 to 150.

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[ 4 ] A method for producing a hydraulic composition, comprising the step of adding the additive for hydraulic compositions according to [1] or [2] above.

The additive for hydraulic compositions of the present invention has the effect of maintaining the air entrainment performance of the hydraulic composition and improving storage stability.

The method for producing an additive for a hydraulic composition has the effect of producing the additive for a hydraulic composition of the present invention, which maintains the air entrainment performance for the hydraulic composition and has improved storage stability.

The method for producing a hydraulic composition of the present invention includes a step of adding the additive for hydraulic compositions of the present invention, and therefore has the effect of producing a hydraulic composition with good workability since the amount of precipitation derived from the lignin sulfonic acid compound in the additive is small.

The following describes the embodiments of the present invention. However, the present invention is not limited to the following embodiments. Therefore, it should be understood that appropriate modifications and improvements can be made to the following embodiments based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. In the following examples, % means % by mass, and parts means parts by mass, unless otherwise specified.

(1) Additives for hydraulic compositions:
The additive for hydraulic compositions of the present invention contains a lignin sulfonic acid compound (A) and water (C), and further contains 0.05 to 10 mass % of an aromatic nonionic surfactant (B).

By adopting the above-mentioned configuration, this additive for hydraulic compositions maintains the air entrainment performance for hydraulic compositions and improves storage stability.

(1-1) Lignosulfonic acid compound (A):
The lignin sulfonic acid compound (A) functions as a dispersant (lignin sulfonic acid dispersant) for imparting fluidity to hydraulic compositions such as concrete.

This lignin sulfonate compound (A) is derived from lignin, which is one of the main components of plants along with polysaccharides such as cellulose, and is produced, for example, when pulp is produced from plants by the sulfite method (sulfide pulp method), by sulfonating lignin as a by-product. The molecular structure of lignin has a complex three-dimensional mesh structure, and the lignin sulfonate compound (A) obtained by sulfonating lignin also has a complex three-dimensional mesh structure. Thus, lignin sulfonate compound (A) is a by-product derived from natural products (i.e., it contains impurities other than lignin sulfonic acid) and, due to its complex three-dimensional mesh structure, it tends to precipitate a lot during storage.

Specifically, the lignin sulfonic acid compound (A) includes a compound (lignin sulfonic acid) having a skeleton in which the carbon at the α-position of the side chain of the hydroxyphenylpropane structure of lignin is cleaved to introduce a sulfo group. The structure of the skeleton is shown in formula (a).

The lignosulfonic acid compound (A) may include a modified product (modified lignosulfonic acid compound) of a compound having the skeleton represented by the above formula (a). The method (modification method) for obtaining this modified product is not particularly limited, and examples of the method include chemical modification methods such as hydrolysis, alkylation, alkoxylation, sulfonation, sulfonate esterification, sulfomethylation, aminomethylation, and desulfonation, and a method of molecular weight fractionation of the lignosulfonic acid compound by ultrafiltration.

In the present invention, lignin sulfonic acid includes those in the form of salts (i.e., lignin sulfonates). Examples of such salts include monovalent metal salts, divalent metal salts, ammonium salts, and organic ammonium salts.

(1-2) Aromatic nonionic surfactant (B):
The hydraulic composition additive of the present invention is obtained by adding an aromatic nonionic surfactant among surfactants (which often have foaming and defoaming properties) to a lignin sulfonic acid dispersant containing a lignin sulfonic acid compound (A) at a predetermined ratio. By adding an aromatic nonionic surfactant (B) at a predetermined ratio in this way, it is possible to obtain an additive for hydraulic compositions that has improved storage stability while maintaining air entrainment performance for hydraulic compositions. When a surfactant is added to a lignin sulfonic acid dispersant containing a lignin sulfonic acid compound (A), the surfactant may affect the air entrainment performance of the hydraulic composition, and the amount of air entrained in the hydraulic composition may be too large or too small. In this respect, in the present invention, the air entrainment performance is maintained as described above by adding an aromatic nonionic surfactant (B) at a predetermined ratio. Furthermore, it is possible to improve the storage stability of the additive for hydraulic compositions containing a lignin sulfonic acid compound (A).

Here, it is believed that the π-π interaction between the structure derived from phenol contained in the aromatic nonionic surfactant (B) and the structure derived from phenol contained in the lignin sulfonic acid compound (A) contributes efficiently to dispersion stabilization and improves storage stability. This aromatic nonionic surfactant (B) has a small effect on the air entrainment performance of the hydraulic composition (i.e., although surfactants often have foaming and defoaming properties, they are unlikely to contribute to foaming or defoaming), and is therefore effective in solving the problems of the present invention.

The blending ratio of the aromatic nonionic surfactant (B) (ratio to the total amount of the additive for hydraulic compositions) is 0.05 to 10 mass%, preferably 0.2 to 5 mass%. By setting the blending ratio in this range, it is possible to obtain an additive for hydraulic compositions that maintains the air entrainment performance for the hydraulic composition and has improved storage stability.

Specifically, the aromatic nonionic surfactant (B) contains at least one selected from the group consisting of aromatic nonionic surfactant (B1) which is a compound represented by the following general formula (1), aromatic nonionic surfactant (B2) which is a compound obtained by condensing a compound represented by the following general formula (2) with a carbonyl compound, and aromatic nonionic surfactant (B3) which is a compound represented by the following general formula (3). With these, it is possible to obtain an additive for hydraulic compositions which further improves storage stability while further maintaining the air entrainment performance for the hydraulic composition.

（一般式（１）において、Ｒ^１は、炭素数７～３０のアルキルフェニル基、又は炭素数１４～３０のスチレン化フェニル基である。Ａ^１Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｍは、Ａ^１Ｏの平均付加モル数であり、１～２００の数である。Ｒ^２は、水素原子、又は炭素数１～６の炭化水素基である。）

(In general formula (1), R ¹ is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone, or two or more types may be used). m is the average number of moles of A ¹ O added, and is a number from 1 to 200. R ² is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.)

（一般式（２）において、Ｒ^３は、炭素数７～３０のアルキルフェニル基、又は炭素数１４～３０のスチレン化フェニル基である。Ａ^２Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｎは、Ａ^２Ｏの平均付加モル数であり、１～２００の数である。Ｒ^４は、水素原子、又は炭素数１～６の炭化水素基である。）

(In general formula (2), R ³ is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. A ² O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone, or two or more types may be used). n is the average number of moles of A ² O added, and is a number from 1 to 200. R ⁴ is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.)

（一般式（３）において、Ｒ^５は、ビスフェノールから２個のヒドロキシ基を除いた残基である。Ａ^３Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｐは、Ａ^３Ｏの平均付加モル数であり、１～２００の数である。Ｒ^６は、水素原子、又は炭素数１～６の炭化水素基である。）

(In general formula (3), R ⁵ is a residue obtained by removing two hydroxyl groups from a bisphenol. A ³ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone or two or more types may be used). p is the average number of moles of A ³ O added and is a number from 1 to 200. R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)

The aromatic nonionic surfactants (B1) to (B3) are described in detail below.

(1-2a) Aromatic nonionic surfactant (B1):
The aromatic nonionic surfactant (B1) is an aromatic nonionic surfactant which is a compound represented by the following general formula (1).

（一般式（１）において、Ｒ^１は、炭素数７～３０のアルキルフェニル基、又は炭素数１４～３０のスチレン化フェニル基である。Ａ^１Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｍは、Ａ^１Ｏの平均付加モル数であり、１～２００の数である。Ｒ^２は、水素原子、又は炭素数１～６の炭化水素基である。）

(In general formula (1), R ¹ is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone, or two or more types may be used). m is the average number of moles of A ¹ O added, and is a number from 1 to 200. R ² is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.)

By including the aromatic nonionic surfactant (B1), it is possible to obtain an additive for hydraulic compositions that further maintains the air entrainment performance for the hydraulic composition while further improving storage stability.

R ¹ in general formula (1) is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms, preferably a styrenated phenyl group having 14 to 30 carbon atoms. In this way, it is possible to obtain an additive for hydraulic compositions which further maintains the air entrainment performance for the hydraulic composition and further improves the storage stability. In one embodiment of the present invention, R ¹ is a styrenated phenyl group having 14 to 30 carbon atoms and R ² is a hydrogen atom.

In general formula (1), A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type alone or two or more types may be used). Preferably, A ¹ O is oxyethylene groups in a total amount of 30 mol % or more, more preferably oxyethylene groups in a total amount of 45 mol % or more, and particularly preferably oxyethylene groups in a total amount of 80 mol % or more. Within such a range, it is possible to obtain an additive for hydraulic compositions which further maintains the air entrainment performance for the hydraulic composition while further improving the storage stability.

In general formula (1), m is the average number of moles of A ¹ O added, and is a number from 1 to 200. And, m is preferably a number from 3 to 150, and more preferably from 5 to 100. Within such a range, it is possible to obtain an additive for a hydraulic composition which further maintains the air entrainment performance for the hydraulic composition and further improves the storage stability.

^R2 in general formula (1) is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom. With such a constitution, it is possible to obtain an additive for hydraulic compositions which further maintains the air entrainment performance for the hydraulic composition and further improves the storage stability.

(1-2b) Aromatic nonionic surfactant (B2):
The additive for hydraulic composition of the present invention contains an aromatic nonionic surfactant (B2) obtained by condensing a compound represented by the following general formula (2) with a carbonyl compound. In other words, the aromatic nonionic surfactant (B2) is a compound having a structure formed by condensing a compound represented by the general formula (2) with a carbonyl compound.

In general formula (2), R ³ is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. A ² O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone, or two or more types may be used). n is the average number of moles of A ² O added, and is a number from 1 to 200. R ⁴ is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.

By including the aromatic nonionic surfactant (B2), it is possible to obtain an additive for hydraulic compositions that further maintains the air entrainment performance for the hydraulic composition while further improving storage stability.

The aromatic nonionic surfactant (B2) preferably has an average condensation degree of 1.1 to 5.0, more preferably 1.2 to 4.0. In one embodiment of the present invention, the aromatic nonionic surfactant (B2) has an average condensation degree of 1.1 to 5.0. By setting the average condensation degree within such a range, it is possible to obtain an additive for hydraulic compositions which further improves storage stability while further maintaining air entrainment performance for hydraulic compositions.

The average condensation degree of the aromatic nonionic surfactant (B2) can be calculated by measuring the following mass average molecular weights by gel permeation chromatography (GPC) and using the formula: Average condensation degree = mass average molecular weight of aromatic nonionic surfactant (B2) ÷ (mass average molecular weight of the compound represented by general formula (2) + mass molecular weight of the carbonyl compound).

The aromatic nonionic surfactant (B2) is a condensation reaction product obtained by condensing a compound represented by general formula (2) with a carbonyl compound, and is a compound containing a structure derived from the compound represented by general formula (2) and a structure derived from a carbonyl compound. In other words, the aromatic nonionic surfactant (B2) in the present invention can also be said to be a compound containing a structure derived from an alkylphenyl compound or a structure derived from a styrenated phenyl compound, an alkylene oxide structure, and a structure derived from a carbonyl compound.

(1-2b-1) Compound represented by formula (2):
R ³ in general formula (2) is an alkylphenyl group having 7 to 30 carbon atoms or a styrenated phenyl group having 14 to 30 carbon atoms, preferably an alkylphenyl group having 10 to 16 carbon atoms or a styrenated phenyl group having 14 to 30 carbon atoms, and more preferably a styrenated phenyl group having 14 to 30 carbon atoms. In this way, it is possible to obtain an additive for hydraulic compositions which further improves storage stability while further maintaining air entrainment performance for hydraulic compositions. In one embodiment of the present invention, R ³ is an alkylphenyl group having 10 to 16 carbon atoms or a styrenated phenyl group having 14 to 30 carbon atoms and R ⁴ is a hydrogen atom.

In general formula (2), A ² O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type alone or two or more types may be used). Preferably, 30 mol % or more of the total amount of A ² O is an oxyethylene group, more preferably 45 mol % or more of the total amount is an oxyethylene group, and particularly preferably 80 mol % or more of the total amount is an oxyethylene group. Within such a range, it is possible to obtain an additive for hydraulic compositions which further maintains the air entrainment performance for the hydraulic composition while further improving the storage stability.

In general formula (2), n is the average number of moles of A ² O added, and is a number from 1 to 200. And, n is preferably a number from 3 to 150, and more preferably from 5 to 100. When it is in such a range, it is possible to obtain an additive for a hydraulic composition which further maintains the air entrainment performance for the hydraulic composition and further improves the storage stability.

^R4 in general formula (2) is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom. With such a constitution, it is possible to obtain an additive for hydraulic compositions which further maintains the air entrainment performance for the hydraulic composition and further improves the storage stability.

(1-2b-2) Carbonyl compounds:
The carbonyl compound is not particularly limited, and examples thereof include formaldehyde, acetaldehyde, benzaldehyde, acetone, and methyl ethyl ketone. Among these, formaldehyde is preferred. When formaldehyde is used, the condensation reaction product of the aromatic nonionic activator (B2) is produced well (in high yield), and the storage stability of the lignin sulfonic acid compound (A) is improved.

(1-2c) Aromatic nonionic surfactants (B3):
The aromatic nonionic surfactant (B3) is an aromatic nonionic surfactant which is a compound represented by the following general formula (3).

（一般式（３）において、Ｒ^５は、ビスフェノールから２個のヒドロキシ基を除いた残基である。Ａ^３Ｏは、炭素数２～４のオキシアルキレン基（但し、当該オキシアルキレン基が複数存在する場合、１種単独又は２種以上とすることができる）である。ｐは、Ａ^３Ｏの平均付加モル数であり、１～２００の数である。Ｒ^６は、水素原子、又は炭素数１～６の炭化水素基である。）

(In general formula (3), R ⁵ is a residue obtained by removing two hydroxyl groups from a bisphenol. A ³ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone or two or more types may be used). p is the average number of moles of A ³ O added and is a number from 1 to 200. R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)

By including the aromatic nonionic surfactant (B3), it is possible to obtain an additive for hydraulic compositions that further maintains the air entrainment performance for the hydraulic composition while further improving storage stability.

^R5 in general formula (3) is a residue obtained by removing two hydroxy groups from bisphenol, and is preferably a residue obtained by removing two hydroxy groups from bisphenol A or bisphenol S. In this way, it is possible to obtain an additive for hydraulic compositions which further improves storage stability while further maintaining air entrainment performance for hydraulic compositions. In one embodiment of the present invention, R5 ^is a residue obtained by removing two hydroxy groups from bisphenol A or bisphenol S, and R6 ^is a hydrogen atom.

In general formula (3), A ³ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type alone or two or more types may be used). Preferably, 30 mol % or more of the total amount of A ³ O is an oxyethylene group, more preferably 45 mol % or more of the total amount is an oxyethylene group, and particularly preferably 80 mol % or more of the total amount is an oxyethylene group. Within such a range, it is possible to obtain an additive for hydraulic compositions which further maintains the air entrainment performance for the hydraulic composition while further improving the storage stability.

In general formula (3), p is the average number of moles of A ³ O added, and is a number from 1 to 200. And, p is preferably a number from 3 to 150, and more preferably from 5 to 100. When it is in such a range, it is possible to obtain an additive for a hydraulic composition which further maintains the air entrainment performance for the hydraulic composition and further improves the storage stability.

^R6 in general formula (3) is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom. With such a constitution, it is possible to obtain an additive for hydraulic compositions which further maintains the air entrainment performance for the hydraulic composition and further improves the storage stability.

Two or more of the aromatic nonionic surfactants (B1) to (B3) may be used simultaneously, and there are no particular restrictions on the content ratio of each, as long as the total of these (i.e., the ratio of the aromatic nonionic surfactant (B)) is in the range of 0.05 to 10 mass%. For example, the content ratio of each of the aromatic nonionic surfactants (B1) to (B3) can be 0.05 to 10 mass%.

(1-3) Water (C):
The water (C) is not particularly limited, and any water that is used in conventional additives for hydraulic compositions, such as lignin sulfonic acid-based dispersants, can be appropriately used.

There are no particular limitations on the mixing ratio of water (C) (ratio to the total amount of additives for hydraulic compositions), but it can be, for example, 10 to 99 mass %.

Conventional lignin sulfonate-based dispersants, which are aqueous liquids containing water like the additive for hydraulic compositions of the present invention, have low stability and are prone to large amounts of precipitation, but in the present invention, by including the above-mentioned aromatic nonionic surfactant (B) in a specified ratio, it is possible to suppress the occurrence of precipitation and improve storage stability.

(1-4) Other components:
The additive for hydraulic compositions of the present invention may further contain other components in addition to the lignin sulfonic acid compound (A), the aromatic nonionic surfactant (B), and water (C).

Other components include, for example, sodium gluconate, polycarboxylic acid dispersants, sugars, rust inhibitors, shrinkage reducing agents, defoamers, air entraining agents, preservatives, thickeners, etc.

The content ratio of the other components can be, for example, 0 to 50% by mass, preferably 0 to 25% by mass, and more preferably 0 to 15% by mass, relative to the total amount of the additive for hydraulic compositions.

(2) Manufacturing method of additive for hydraulic composition:
The method for producing an additive for a hydraulic composition includes a mixing step of blending a lignin sulfonic acid compound (A), an aromatic nonionic surfactant (B), and water (C) so that the aromatic nonionic surfactant (B) is contained in an amount of 0.05 to 10 mass % of the total.

According to this method for producing an additive for hydraulic compositions, it is possible to produce the additive for hydraulic compositions of the present invention that maintains the air entrainment performance for the hydraulic composition and has improved storage stability.

(2-1) Mixing step:
In this step, the lignin sulfonic acid compound (A), the aromatic nonionic surfactant (B), and the water (C) may all be mixed together, or a portion of each may be mixed first and then the remaining portion may be mixed in. For example, the lignin sulfonic acid compound (A) and the water (C) may be mixed, and then the aromatic nonionic surfactant (B) may be mixed.

The proportion of the aromatic nonionic surfactant (B) in the entire hydraulic composition additive is 0.05 to 10 mass%, preferably 0.2 to 5 mass%. By setting the proportion in this manner, it is possible to obtain an additive for hydraulic compositions that maintains the air entrainment performance for the hydraulic composition and has improved storage stability.

There are no particular limitations on the method for mixing the components, and any conventional method can be used as appropriate.

For example, the mixing temperature can be between 5 and 80°C.

(3) Hydraulic composition:
The additive for hydraulic compositions of the present invention is used by being added to hydraulic compositions.

This hydraulic composition, like conventionally known hydraulic compositions, contains a binder (hydraulic binder), water, fine aggregate, coarse aggregate, etc.

The content ratio of the additive for hydraulic compositions of the present invention in this hydraulic composition is not particularly limited and can be set appropriately. For example, the content ratio of the additive for hydraulic compositions of the present invention can be 0.01 to 5.0 parts by mass per 100 parts by mass of the binder.

Examples of binders include various types of Portland cement, such as ordinary Portland cement, moderate heat Portland cement, low heat Portland cement, high early strength Portland cement, and sulfate-resistant Portland cement, as well as various types of cement, such as blast furnace cement, fly ash cement, and silica fume cement.

Furthermore, the binder may be used in combination with various admixtures such as fly ash, ground granulated blast furnace slag, ground limestone, stone powder, silica fume, and expansive agents.

Fine aggregates include, for example, river sand, mountain sand, land sand, sea sand, silica sand, crushed sand, various types of slag fine aggregates, etc., but may also contain fine particles such as clay.

Examples of coarse aggregates include river gravel, mountain gravel, land gravel, crushed stone, various types of slag coarse aggregate, lightweight aggregate, etc.

The hydraulic composition may further contain other components as appropriate, provided that the effect is not impaired. Examples of such other components include setting retarders made of sugars, oxycarboxylates, etc., various fluidizing agents, air entraining agents made of anionic surfactants, antifoaming agents made of oxyalkylene compounds, hardening accelerators made of alkanolamines, shrinkage reducers made of polyoxyalkylene alkyl ethers, thickeners made of cellulose ether compounds, quick-setting agents made of calcium sulfonates, preservatives made of isothiazolinone compounds, and rust inhibitors made of nitrites.

The content ratio of other components can be, for example, 0 to 5 parts by weight per 100 parts by weight of binder.

The ratio of water to binder in the hydraulic composition (water/binder ratio) can be any ratio known in the art, but can be, for example, 20 to 70% by mass, and preferably 30 to 65% by mass.

(4) Method for producing hydraulic composition:
The method for producing a hydraulic composition of the present invention includes a step of adding the additive for hydraulic composition of the present invention (additive adding step). According to this method for producing a hydraulic composition, by including a step of adding the additive for hydraulic composition of the present invention, the amount of precipitate derived from the lignosulfonic acid compound in the additive is small, so that the hydraulic composition can be produced with good workability. That is, when a large amount of precipitate derived from the lignosulfonic acid compound is present in the additive for hydraulic composition containing the lignosulfonic acid compound, it is troublesome to stir the additive for hydraulic composition before use to dissolve the precipitate. In addition, if the additive for hydraulic composition is used while the precipitate remains, it is considered that the precipitate will eventually be removed. These operations tend to be troublesome in producing a hydraulic composition. On the other hand, if the amount of precipitate derived from the lignosulfonic acid compound is small, the above-mentioned operations can be omitted, and the hydraulic composition can be produced with good workability.

In the additive addition step, the method of adding the additive for the hydraulic composition of the present invention is not particularly limited, and any conventionally known method can be appropriately adopted.

In addition, when producing the hydraulic composition, the binders and other components constituting the hydraulic composition can be appropriately mixed by conventionally known methods. Examples of components such as binders include those mentioned above.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

First, the lignosulfonic acid compounds (A) (LS-1 to LS-3) used in the examples and comparative examples are shown in Table 1 below.

Next, the aromatic nonionic surfactants (B) (B1-1 to B1-11, B2-1 to B2-4, B3-1 to B3-3, BR-1, BR-2) used in the examples and comparative examples are shown in Tables 2 to 4 below.

In Tables 2 and 3, the number of moles of oxyethylene (EO) added and the number of moles of oxypropylene (PO) added are calculated values assuming that each main component of styrenated phenol (specifically, monostyrenated phenol (mono form), distyrenated phenol (di form), and tristyrenated phenol (tri form)) is 100. Note that each main component of the mono-, di-, and tri-forms is a group shown in the "R ¹ " column in Table 2 and the "R ³ " column in Table 3. For example, in the case of B1-1 in Table 2, it is "monostyrenated phenol" which becomes a monostyrenated phenyl group.

In Table 2, "BR-1" is a commercially available lauryl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) to which 6 moles of ethylene oxide have been added. "BR-2" is Mighty 150 (manufactured by Kao Corporation) used as is. In Table 2, "EO" stands for ethylene oxide and "PO" stands for propylene oxide. In Table 2, "random" in the "addition form" column means that the alkylene oxide was added randomly.

(Synthesis Example 1)
Aromatic nonionic surfactants (B1-1) to (B1-3), (B1-5), and (B1-6)
309.8 g of monostyrenated phenol "SP-F" (manufactured by Sankosha) and 4.2 g of 48% aqueous potassium hydroxide solution were added to an autoclave, and the inside of the autoclave was fully replaced with nitrogen, and then dehydration was performed under reduced pressure at 120°C while stirring. Thereafter, 688.2 g of ethylene oxide was injected at a gauge pressure of 0.4 MPa at this temperature and reacted, and the reaction was completed by aging at the above temperature for 1 hour. Thereafter, neutralization filtration was performed using Kyoward 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) to obtain an aromatic nonionic surfactant (B1-1).

In addition, "SP-F (product name) manufactured by Sankosha" is a compound that is composed of 65 mol % or more of mono-styrenated phenol (i.e., monostyrenated phenol), 32 mol % or less of di-styrenated phenol (i.e., distyrenated phenol), and 1 mol % or less of tri-styrenated phenol (i.e., tristyrenated phenol).

(Synthesis Examples 2, 3, 5, and 6)
Aromatic nonionic surfactants (B1-2), (B1-3), (B1-5), (B1-6)
Aromatic nonionic surfactants (B1-2), (B1-3), (B1-5), and (B1-6) were obtained in the same manner as in Synthesis Example 1, except that "TSP" (manufactured by Sankosha) was used in the case of a tristyrenated phenyl group, and "SP-24" (manufactured by Sankosha) was used in the case of a distyrenated phenyl group.

"Sankosha's SP-24 (product name)" is a compound that is 0 mol% mono (i.e., monostyrenated phenol), 60 mol% or more di (i.e., distyrenated phenol), and 40 mol% or less tri (i.e., tristyrenated phenol). "Sankosha's TSP (product name)" is a compound that is 0 mol% mono (i.e., monostyrenated phenol), 30 mol% or less di (i.e., distyrenated phenol), and 65 mol% or more tri (i.e., tristyrenated phenol).

(Synthesis Example 4)
Aromatic nonionic surfactants (B1-4)
131.2 g of tristyrenated phenol "TSP" (manufactured by Sankosha) and 3.2 g of 48% aqueous potassium hydroxide solution were added to the autoclave, and the inside of the autoclave was fully replaced with nitrogen, and then dehydration was performed under reduced pressure at 120°C while stirring. Then, at this temperature, 1179.9 g of ethylene oxide and 187.4 g of propylene oxide were simultaneously injected at a gauge pressure of 0.4 MPa to react, and the reaction was completed by aging at the above temperature for 1 hour. Then, neutralization filtration was performed using Kyoward 600 to obtain an aromatic nonionic surfactant (B1-4).

(Synthesis Examples 7, 8, 10, and 11)
Aromatic nonionic surfactants (B1-7), (B1-8), (B1-10), (B1-11)
Aromatic nonionic surfactants (B1-7), (B1-8), (B1-10), and (B1-11) were obtained in the same manner as in Synthesis Example 4, except that "paraoctylphenol (POP)" (manufactured by Maruzen Petrochemical Co., Ltd.) was used in the case of an octylphenyl group, and "SP-24" (manufactured by Sankosha Co., Ltd.) was used in the case of a distyrenated phenyl group.

(Synthesis Example 9)
Aromatic nonionic surfactants (B1-9)
In the same manner as in Synthesis Example 1, a reaction product was obtained by adding 105 moles of ethylene oxide to tristyrenated phenol. Thereafter, 503.2 g of the reaction product was again charged into the autoclave, and 6.2 g of potassium hydroxide was added, followed by dehydration under reduced pressure at 120°C. Thereafter, 5.1 g of methyl chloride was reacted at 90°C. After completion of the reaction, the mixture was aged at this temperature for 4 hours to complete the reaction. Thereafter, neutralization and desalting treatment were performed to obtain an aromatic nonionic surfactant (B1-9).

In Table 3, "EO" stands for ethylene oxide, and "PO" stands for propylene oxide. In Table 3, "block" in "addition form" means that alkylene oxide is block-added.

(Synthesis Example 10)
Aromatic nonionic surfactants (B2-1)
406.6 g of tristyrenated phenol "TSP" (manufactured by Sankosha), 3.8 g of p-toluenesulfonic acid monohydrate, and 18.0 g of paraformaldehyde were added to the autoclave, and condensed at 110 ° C. for 3 hours while refluxing. Then, 7.8 g of 48% potassium hydroxide aqueous solution was added, and the inside of the autoclave was sufficiently replaced with nitrogen, and then dehydration was performed under reduced pressure at 120 ° C. while stirring. Then, at this temperature, 2068.0 g of ethylene oxide was injected at a gauge pressure of 0.4 MPa to react, and the reaction was completed by aging at the above temperature for 1 hour. Then, neutralization filtration was performed using Kyoward 600 to obtain an aromatic nonionic surfactant (B2-1).

(Synthesis Example 11)
Aromatic nonionic surfactants (B2-2)
302.4 g of distyrenated phenol "SP-24" (manufactured by Sankosha), 1.9 g of methanesulfonic acid, and 30.0 g of paraformaldehyde were added to the autoclave, and condensed at 110 ° C. for 3 hours while refluxing. Then, 4.1 g of 48% potassium hydroxide aqueous solution was added, and the inside of the autoclave was sufficiently replaced with nitrogen, and then dehydration was performed under reduced pressure at 120 ° C. while stirring. Then, at this temperature, 352 g of ethylene oxide and 58.1 g of propylene oxide were simultaneously injected at a gauge pressure of 0.4 MPa and reacted, and the reaction was completed by aging at the above temperature for 1 hour. Then, neutralization filtration was performed using Kyoward 600 to obtain an aromatic nonionic surfactant (B2-2).

(Synthesis Example 12)
Aromatic nonionic surfactants (B2-3)
206.3 g of octylphenol "paraoctylphenol (POP)" (Maruzen Petrochemical Co., Ltd.), 3.8 g of p-toluenesulfonic acid monohydrate, and 206.3 g of paraformaldehyde were added to the autoclave, and condensed at 110 ° C. for 5 hours while refluxing. Then, 6.8 g of 48% potassium hydroxide aqueous solution was added, and the inside of the autoclave was sufficiently replaced with nitrogen, and then dehydration was performed under reduced pressure at 120 ° C. while stirring. Then, at this temperature, 1760 g of ethylene oxide was injected at a gauge pressure of 0.4 MPa and reacted, and then 116.0 g of propylene oxide was injected at a gauge pressure of 0.4 MPa and reacted, and the reaction was completed by aging at the above temperature for 1 hour. Then, neutralization filtration was performed using Kyoward 600 to obtain an aromatic nonionic surfactant (B2-3).

(Synthesis Example 13)
Aromatic nonionic surfactants (B2-4)
An aromatic nonionic surfactant (B2-4) was obtained in the same manner as in Synthesis Example 11, except that tristyrenated phenol "TSP" (manufactured by Sankosha) was used instead of distyrenated phenol "SP-24" (manufactured by Sankosha).

In Table 4, "EO" stands for ethylene oxide, and "PO" stands for propylene oxide. In Table 4, "block" in "addition form" means that alkylene oxide is block-added.

(Synthesis Example 14)
Aromatic nonionic surfactants (B3-1)
318.9 g of "Newpol BPE-60" (manufactured by Sanyo Chemical Industries, Ltd.), which is an adduct of 6 moles of ethylene oxide added to all hydroxyl groups of 2,2-bis(4-hydroxyphenyl)propane, and 3.0 g of potassium hydroxide were added to an autoclave, and the inside of the autoclave was thoroughly replaced with nitrogen, and then dehydration was carried out under reduced pressure at 120°C while stirring. Then, 2681.1 g of ethylene oxide was injected at a gauge pressure of 0.4 MPa at this temperature to react, and the reaction was completed by aging for 1 hour at the above temperature. Then, the mixture was neutralized and filtered using Kyoward 600 to obtain an aromatic nonionic surfactant (B3-1).

(Synthesis Example 15)
Aromatic nonionic surfactants (B3-2)
250.3 g of commercially available bis(4-hydroxyphenyl)sulfone (Tokyo Chemical Industry Co., Ltd.) and 8.0 g of potassium tert-butoxide were added to the autoclave, and the inside of the autoclave was sufficiently replaced with nitrogen, and then the temperature was raised to 120 ° C. while stirring. Then, 176 g of ethylene oxide was charged at this temperature, and the reaction was started. After confirming that the pressure had decreased, 5544.0 g of ethylene oxide was further injected into the reaction system at a gauge pressure of 0.4 MPa and reacted, and then 580.0 g of propylene oxide was further injected at a gauge pressure of 0.4 MPa and reacted, and the reaction was completed by aging at the above temperature for 1 hour. Then, the mixture was neutralized and filtered using Kyoward 600 to obtain an aromatic nonionic surfactant (B3-2).

(Synthesis Example 16)
Aromatic nonionic surfactants (B3-3)
An aromatic nonionic surfactant (B3-3) was obtained in the same manner as in Synthesis Example 14, except that the amount of ethylene oxide was changed so as to satisfy Table 4.

(Average Condensation Degree)
For the prepared aromatic nonionic surfactants (B2) ((B2-1) to (B2-3)), the weight average molecular weight was measured by gel permeation chromatography (GPC) under the measurement conditions shown below, and the average condensation degree was calculated using the following formula.

<Method of calculating average condensation degree>
Average condensation degree = mass average molecular weight of aromatic nonionic surfactant (B2) ÷ (mass average molecular weight of compound represented by general formula (2) + mass molecular weight of carbonyl compound)

<Conditions for measuring weight average molecular weight>
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK gel Super H4000 + TSK gel Super H3000 + TSK gel Super H2000 (manufactured by Tosoh Corporation)
Detector: differential refractometer (RI)
Eluent: tetrahydrofuran Flow rate: 0.5 mL/min Column temperature: 40° C.
Sample concentration: Eluent solution with a sample concentration of 0.5% by mass Standard material: Polystyrene (manufactured by Tosoh Corporation)

Next, the polycarboxylic acid-based dispersants (referred to as "PCE" in Table 5) (PC-1 to PC-4) used when preparing the hydraulic composition using formulation (2) are shown in Table 5 below.

In Table 5, "M-1" to "M-4", "AAA", "MA", and "HEA" are specifically shown below.
M-1: α-methacrylic-ω-methoxy-poly(9 mol)oxyethylene M-2: α-(3-methyl-3-butenyl)-ω-hydroxy-poly(50 mol)oxyethylene M-3: α-methallyl-ω-hydroxy-poly(113 mol)oxyethylene M-4: α-methacrylic-ω-methoxy-poly(45 mol)oxyethylene MAA: methacrylic acid AA: acrylic acid MA: methyl acrylate HEA: hydroxyethyl acrylate

(Synthesis Example 17)
1. Method for Producing Polycarboxylic Acid Dispersant (Reaction Mixture (PC-1)) 148.1 g of α-methacryl-ω-methoxy-poly(9 mol)oxyethylene, 30.0 g of methacrylic acid, 9.4 g of methyl acrylate, 4.1 g of 3-mercaptopropionic acid and 181.0 g of ion-exchanged water were charged into a reaction vessel having an internal volume of 1 L, and after uniformly dissolving with stirring, the atmosphere was replaced with nitrogen. The temperature of the reaction system was kept at 60° C. in a hot water bath, and 31.4 g of a 6.2% aqueous solution of sodium persulfate was dropped to start polymerization, and the polymerization reaction was continued for 6 hours to complete the polymerization. After cooling, a 30% aqueous solution of sodium hydroxide was added to obtain a pH of 7, and the concentration was further adjusted to 40% with ion-exchanged water to obtain a polycarboxylic acid dispersant (PC-1) which is the reaction mixture (PC-1). When this reaction mixture (PC-1) was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 18,600.

(Synthesis Example 18)
Method for producing polycarboxylic acid-based dispersant (reaction mixture (PC-2)) 102.6 g of ion-exchanged water and 180.6 g of α-(3-methyl-3-butenyl)-ω-hydroxy-poly(n = 50)oxyethylene were charged into a reaction vessel with an internal volume of 1 L, and after uniform dissolution with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was set to 65 ° C. in a hot water bath. Thereafter, a solution obtained by diluting 15.7 g of acrylic acid with 76.5 g of ion-exchanged water was dropped over 3 hours, and at the same time, 9.8 g of 3.5% hydrogen peroxide solution was dropped into the reaction system over 3 hours, and at the same time, a solution obtained by diluting 0.8 g of 3-mercaptopropionic acid and 0.8 g of L-ascorbic acid with 6.3 g of ion-exchanged water was dropped into the reaction system over 4 hours. The temperature of the reaction system was further maintained at 65 ° C. and aged for 1 hour. The pH was adjusted to 5 using a 30% aqueous sodium hydroxide solution, and the concentration was adjusted to 40% using ion-exchanged water to obtain a polycarboxylic acid dispersant (PC-2) which is a reaction mixture (PC-2). When this reaction mixture (PC-2) was analyzed by gel permeation chromatography (GPC), it was found to have a mass average molecular weight of 32,000.

(Synthesis Example 19)
Method for producing polycarboxylic acid-based dispersant (reaction mixture (PC-3)) 151.0 g of ion-exchanged water and 177.0 g of α-methallyl-ω-hydroxy-oxypropylene poly(113 mol)oxyethylene were added to a reaction vessel with an internal volume of 1 L, and after uniform dissolution with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was set to 70 ° C. in a hot water bath. A solution obtained by diluting 11.8 g of acrylic acid and 7.9 g of hydroxyethyl acrylate with 31.5 g of ion-exchanged water was dropped over 3 hours, and at the same time, 8.9 g of 3.5% hydrogen peroxide solution was dropped into the reaction system over 3 hours, and at the same time, a solution obtained by diluting 1.0 g of 3-mercaptopropionic acid and 0.8 g of L-ascorbic acid with 7.1 g of ion-exchanged water was dropped into the reaction system over 4 hours. The temperature of the reaction system was further maintained at 60 ° C. and aged for 0.5 hours. The pH was adjusted to 7 using a 30% aqueous sodium hydroxide solution, and the concentration was adjusted to 40% using ion-exchanged water to obtain a polycarboxylic acid dispersant (PC-3), which is a reaction mixture (PC-3). When this reaction mixture (PC-3) was analyzed by gel permeation chromatography (GPC), it was found to have a mass average molecular weight of 39,000.

(Synthesis Example 20)
Manufacturing method of polycarboxylic acid dispersant (reaction mixture (PC-4)) 103.4g of ion-exchanged water was added to a reaction vessel with an internal volume of 1L, the atmosphere was replaced with nitrogen while stirring, and the temperature of the reaction system was set to 65 ° C. in a warm water bath. An aqueous solution of 311.7g of α-methacrylic-ω-methoxy-poly (45 mol) oxyethylene, 77.9g of methacrylic acid, and 2.7g of 3-mercaptopropionic acid dissolved in 342.5g of ion-exchanged water was dropped over 3 hours, and at the same time, 24.3g of 7% hydrogen peroxide solution was dropped over 4 hours. The temperature of the reaction system was further maintained at 65 ° C. and aged for 1 hour. A 30% aqueous sodium hydroxide solution was added to adjust the pH to 5.6, and the concentration was adjusted to 40% with ion-exchanged water to obtain a polycarboxylic acid dispersant (PC-4) which is a reaction mixture (PC-4). When this reaction mixture (PC-4) was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 35,000.

(Method of measuring mass average molecular weight)
The method for measuring the mass average molecular weight of the reaction mixtures (PC-1) to (PC-4) was as follows.
Apparatus: Shodex GPC-101 (manufactured by Showa Denko Co., Ltd.)
Column: OHpak SB-806M HQ + SB-806M HQ (Showa Denko)
Detector: differential refractometer (RI)
Eluent: 50 mM sodium nitrate aqueous solution Flow rate: 0.7 mL/min Column temperature: 40° C.
Sample concentration: Eluent solution with a sample concentration of 0.5% by mass Standard substances: polyethylene glycol, polyethylene oxide (Agilent)

(Examples 1 to 30, Comparative Examples 1 to 7)
(1) Preparation of additive for hydraulic composition:
The lignin sulfonic acid compound (A), the aromatic nonionic surfactant (B) produced as described above, and water (C) were mixed in the types and ratios shown in Tables 6 and 7 below to prepare additives for hydraulic compositions (L-1 to L-30, R-1 to R-7). Tap water (Gamagori City tap water) was used as the mixing water other than the water contained in each component, and in Examples 6 and 27, sodium gluconate (reagent: manufactured by Kishida Chemical Co., Ltd.) (denoted as "GS" in Table 6) was mixed as another component. In Examples 24 to 30 and Comparative Example 7, polycarboxylic acid dispersants (PC-1) to (PC-4) shown in Table 7 were further mixed in a predetermined mixing ratio as another component.

In Tables 6 and 7, for example, in Example 10, "B1-1/B2-1" for aromatic nonionic surfactant (B) means that aromatic nonionic surfactants (B1-1) and (B2-1) are blended together. In Example 10, "1.0/0.5" in "% by mass" means that 1.0% by mass of aromatic nonionic surfactant (B1-1) and 0.5% by mass of aromatic nonionic surfactant (B2-1) are blended together.

(2) Preparation of hydraulic composition (concrete composition):
Next, hydraulic compositions were prepared using the prepared additives for hydraulic compositions (L-1 to L-30, R-1 to R-7) as follows. Table 8 shows the mix conditions of the hydraulic compositions (concrete compositions), mix (1) and mix (2).

First, the mix (1) will be described below. In a thermostatic room at 20°C and humidity of 80%, under the mix conditions shown in Table 8, a 55-L pan-type forced mixer was used to mix the concrete with a hydraulic binder consisting of ordinary Portland cement (an equal mixture of Pacific Cement Corporation, Ube Mitsubishi Cement Corporation, and Sumitomo Osaka Cement Co., Ltd., density = 3.16 g/cm ³ ), fine aggregate (Oigawa River water system sand and land sand, density = 2.58 g/cm ³ ) and coarse aggregate (Okazaki crushed stone, density = 2.68 g/cm ^{3 ).} ), and further, 0.4 mass% of additives for hydraulic compositions (L-1 to L-23, R-1 to R-6) based on cement, 0.2 mass% of 10 mass% aqueous solution of sodium gluconate (Kishida Chemical Co., Ltd.) based on cement, and 0.002 mass% of commercially available air-enhancing agent "AE-300 (Takemoto Yushi Co., Ltd.)" based on cement were measured as a part of mixing water (tap water), and the mixture was put into a mixer and mixed for 60 seconds to prepare 30 L of hydraulic compositions (concrete compositions) of Examples 1 to 23 and Comparative Examples 1 to 6. At this time, the target air content was set to 4.5% and the target slump was set to 15.5 cm.

The temperature of each material was adjusted before preparation so that the temperature of the mixed concrete composition was within the range of 20±2°C. The temperature of the mixed concrete composition was measured in accordance with JIS-A1156 (2014).

Next, the mix (2) will be described below. In a thermostatic room at 20°C and humidity of 80%, under the mix conditions shown in Table 8, a pan-type forced mixer with a nominal capacity of 55 L was used to mix the concrete with a hydraulic binder consisting of ordinary Portland cement (an equal mixture of Pacific Cement Corporation, Ube Mitsubishi Cement Corporation, and Sumitomo Osaka Cement Co., Ltd., density = 3.16 g/cm ³ ), fine aggregate (Oigawa River water system sand and land sand, density = 2.58 g/cm ³ ) and coarse aggregate (Okazaki crushed stone, density = 2.68 g/cm ^{3 )} . ), and further, 1.0% by mass of additives for hydraulic compositions (L-24 to L-30, R-7) based on cement, 0.002% by mass of a commercially available air entrainer AE-300 (Takemoto Yushi Co., Ltd.) based on cement, and 0.0005% by mass of a commercially available antifoaming agent AFK-2 (Takemoto Yushi Co., Ltd.) based on cement were weighed as part of the mixing water (tap water), charged into a mixer, and mixed for 90 seconds. In this way, 30 L of hydraulic compositions (concrete compositions) of Examples 24 to 30 and Comparative Example 7 were prepared. At this time, the target air content was set to 4.5% and the target slump was set to 18.0 cm.

As with Mixture (1), the temperature of each material was adjusted before preparation so that the temperature of the mixed concrete composition was within the range of 20±2°C. The temperature of the mixed concrete composition was measured in accordance with JIS-A1156 (2014).

Next, various evaluations were performed on the prepared hydraulic compositions (stability, slump, air content (%), difference from standard for air content, AE property, and overall evaluation). The evaluation results are shown in Tables 6 and 7.

The evaluation methods and evaluation criteria for each of the prepared hydraulic compositions are shown below.

(Stability)
Each of the prepared hydraulic composition additives (L-1 to L-30, R-1 to R-7) was added to a 100 mL Fine oil settling tube (graduated) (Tokyo Glass Instruments Co., Ltd.) up to the 100 mL mark. At this time, each hydraulic composition additive was thoroughly shaken just before being added to the settling tube. Thereafter, the settling tube containing each hydraulic composition additive was left to stand in a room at 25°C, and the degree of settling of the precipitate (amount of sediment) was checked after 14 days.

The stability was evaluated based on the following criteria.
S: When the amount of sediment is 0.5 mL or less A: When the amount of sediment is more than 0.5 mL and less than 1.0 mL B: When the amount of sediment is more than 1.0 mL and less than 2.0 mL C: When the amount of sediment is more than 2.0 mL

(slump)
The hydraulic composition (concrete composition) immediately after mixing was measured in accordance with JIS-A1101 (2020).

(Air volume (%))
The hydraulic composition (concrete composition) immediately after mixing was measured in accordance with JIS-A1128 (2019).

(Difference from standard for air volume)
The difference in air volume from the standard air volume (air volume in Comparative Example 1) was calculated according to the formula: "difference in air volume from standard (%) = air volume in each Example and Comparative Example (%) - standard air volume (%)".

(AE)
In the case of formulation (1) which did not contain an aromatic nonionic surfactant (polycarboxylic acid-based dispersants (PC-1) to (PC-4)), the air amount of Comparative Example 1 was used as the standard, and in the case of formulation (2), the air amount of Comparative Example 7 was used as the standard. Evaluation was performed according to the following evaluation criteria.
S: When the difference between the air volume and the standard is within ±1.0% A: When the difference between the air volume and the standard is more than ±1.0% and within ±1.5% B: When the difference between the air volume and the standard is more than ±1.5% and within ±2.0% C: When the difference between the air volume and the standard is more than ±2.0%

(comprehensive evaluation)
Based on the evaluation results of stability and AE, a comprehensive evaluation was made according to the following criteria.
S: When both stability and AE are S A: When stability and AE are S and A, or A and S B: When either stability or AE is B C: When either stability or AE is C

(result)
As shown in Tables 6 and 7, the hydraulic composition additives of Examples 1 to 30 have better AE properties than the hydraulic composition additives of Comparative Examples 1 to 7, so that they maintain the air entraining performance for the hydraulic composition, and the stability evaluation is good, so that it was confirmed that an additive for a hydraulic composition with improved storage stability can be obtained.

The hydraulic composition additive of the present invention can be used as an additive for hydraulic compositions such as concrete and mortar. The method for producing the hydraulic composition additive of the present invention can be adopted as a method for producing the hydraulic composition additive of the present invention. The hydraulic composition of the present invention can be used to form a hardened hydraulic composition body such as a hardened concrete body or a hardened mortar body.

Claims (7)

A lignosulfonic acid compound (A) and water (C),
The additive for hydraulic compositions further comprises 0.05 to 10 mass % of an aromatic nonionic surfactant (B). The additive for hydraulic compositions according to claim 1, wherein the aromatic nonionic surfactant (B) contains at least one selected from the group consisting of an aromatic nonionic surfactant (B1) which is a compound represented by the following general formula (1), an aromatic nonionic surfactant (B2) which is a compound obtained by condensing a compound represented by the following general formula (2) with a carbonyl compound, and an aromatic nonionic surfactant (B3) which is a compound represented by the following general formula (3).

(In general formula (1), R ¹ is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone, or two or more types may be used). m is the average number of moles of A ¹ O added, and is a number from 1 to 200. R ² is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.)

(In general formula (2), R ³ is an alkylphenyl group having 7 to 30 carbon atoms, or a styrenated phenyl group having 14 to 30 carbon atoms. A ² O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone, or two or more types may be used). n is the average number of moles of A ² O added, and is a number from 1 to 200. R ⁴ is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms.)

(In general formula (3), R ⁵ is a residue obtained by removing two hydroxyl groups from a bisphenol. A ³ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of oxyalkylene groups are present, one type may be used alone or two or more types may be used). p is the average number of moles of A ³ O added and is a number from 1 to 200. R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) In the general formula (1), A ¹ O is an oxyethylene group that accounts for 30 mol % or more of the total amount of A ¹ O, and m is a number from 3 to 150;
In the general formula (2), A ² O is an oxyethylene group that accounts for 30 mol % or more of the total amount of A ² O, and n is a number from 3 to 150;
The additive for hydraulic compositions according to claim 2, wherein A ³ O in the general formula (3) is an oxyethylene group that accounts for 30 mol % or more of the total amount of A ³ O, and p is a number from 3 to 150. In the general formula (1), R ¹ is a styrenated phenyl group having 14 to 30 carbon atoms and R ² is a hydrogen atom;
In the general formula (2), R ³ is an alkylphenyl group having 10 to 16 carbon atoms or a styrenated phenyl group having 14 to 30 carbon atoms, and R ⁴ is a hydrogen atom;
The additive for hydraulic compositions according to claim 2 or 3, wherein ^R5 in the general formula (3) is a residue obtained by removing two hydroxy groups from bisphenol A or bisphenol S, and ^R6 is a hydrogen atom. The additive for hydraulic compositions according to claim 2 or 3, wherein the aromatic nonionic surfactant (B2) has an average degree of condensation of 1.1 to 5.0. A method for producing an additive for hydraulic compositions, comprising a mixing step of blending a lignin sulfonic acid compound (A), an aromatic nonionic surfactant (B), and water (C) so that the aromatic nonionic surfactant (B) is contained in an amount of 0.05 to 10 mass % of the total. A method for producing a hydraulic composition, comprising the step of adding an additive for hydraulic compositions according to any one of claims 1 to 3.