JP7456685B2 - Additives for hydraulic compositions - Google Patents

Description

The present invention relates to additives for hydraulic compositions. More specifically, the present invention relates to an additive for hydraulic compositions that improves the pumpability of hydraulic compositions.

Hydraulic compositions such as concrete are widely used for civil engineering and construction. When such a hydraulic composition is used, cement, water, fine aggregate, coarse aggregate, an admixture, and the like are mixed and stirred to prepare a hydraulic composition kneaded product.

At the construction site, a method of transporting the prepared hydraulic composition kneaded material to the placement position is by using a concrete pump to pump it. In this method, a transport pipe is placed between the pouring position and the concrete pump to form a flow path for the hydraulic composition mixture, and the hydraulic composition mixture in the transport pipe is moved by the pressure generated from the concrete pump. It is pumped to the pouring position.

However, in the method of pressure-feeding using a concrete pump, the resistance between the kneaded hydraulic composition and the surface of the transport pipe increases, which may result in poor discharge or clogging in the transport pipe.

Conventionally, when using a concrete pump to pump a mixed hydraulic composition, lignosulfonate-based AE water-reducing was used to prevent the above-mentioned discharge failure and clogging in the transport pipe and improve pump pumping performance. It has been proposed to incorporate an admixture containing an aminosulfonic acid resin and an aminosulfonic acid resin into a hydraulic composition (for example, see Patent Document 1). Furthermore, it has been proposed to use a biogum-based thickener in pumping concrete using lightweight aggregate, which is difficult to pump (see, for example, Patent Document 2).

Japanese Patent Application Publication No. 8-81248 Japanese Patent Application Publication No. 2000-327393

When the admixture shown in Patent Document 1 is used, pumpability is improved to some extent. However, the lignosulfonate-based AE water reducer and aminosulfonic acid resin that are blended into this admixture are both used as water reducers for cement, so the slump may be adjusted depending on the target concrete. There is a problem that it is difficult.

Moreover, the concrete admixture shown in Patent Document 2 enables pumping by adding a biogum-based thickener to concrete using lightweight aggregate to increase the viscosity. However, when pumping is required over a considerable distance, such as in civil engineering work, it is necessary to increase the viscosity to a certain extent, but there is a problem that increasing the viscosity reduces pumping performance. Furthermore, the degree of effectiveness of thickeners varies depending on the target material, so it is not easy to adjust them. In other words, if even a small amount is added in excess of the optimum amount, the pumping performance will deteriorate. Furthermore, thickeners have the problem of being cumbersome to handle and having poor workability.

In view of the above circumstances, the additive for hydraulic compositions of the present invention can improve the pumpability during pumping with a concrete pump, can obtain a high effect with a small amount, and can improve the hydraulic composition. The object of the present invention is to provide an additive for hydraulic compositions that does not affect slump and air content.

As a result of intensive research to solve the above problems, the present inventors found that an additive for hydraulic compositions containing a specific rosin polyoxyalkylene adduct is particularly suitable. According to the present invention, the following additive for hydraulic compositions is provided.

[1] It is added to a hydraulic composition containing a hydraulic binder and is mixed in a ratio of 0.00001 to 0.1 parts by mass per 100 parts by mass of the hydraulic binder;
The composition contains a compound represented by the following general formula (1) and a dispersant,
The additive for hydraulic compositions used to improve the pumpability of a hydraulic composition, wherein the dispersant is at least one selected from the group consisting of lignin sulfonic acid-based dispersants and polycarboxylic acid-based dispersants.

（但し、一般式（１）中、Ｒ^１は、ロジンのアシル残基又は水素原子を示し（但し、ｎが１の場合、Ｒ^１はロジンのアシル残基を示し、ｎが２以上の場合、Ｒ^１のうち、少なくとも１つはロジンのアシル残基を示す）、Ｒ^２は、水素原子、ロジンのアシル残基、炭素数１～２０のアルキル基、炭素数２～２０のアルケニル基、炭素数３～２０の多価アルコールから水酸基を除いた残基、炭素数１～２０のアシル基又は炭素数２～２０の多価カルボン酸のアシル残基を示し（但し、Ｒ^１の少なくとも一つが水素原子を示す場合、Ｒ^２は、水素原子以外の置換基を示す）、ＡＯは、炭素数２～１８のオキシアルキレン基を示し、
ｍは１～２００の数であって、ｎは１～２０の数であって、かつ、前記ｍ、ｎが、ｍ×ｎ＝１～２００となる関係を満たす数であり、ＡＯの内、炭素数２のオキシアルキレン基が５０モル％以上である。）

(However, in general formula (1), R ¹ represents an acyl residue of rosin or a hydrogen atom (however, when n is 1, R ¹ represents an acyl residue of rosin, and when n is 2 or more) , at least one of R ¹ represents an acyl residue of rosin), R ² is a hydrogen atom, an acyl residue of rosin, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, Represents a residue obtained by removing a hydroxyl group from a polyhydric alcohol having 3 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, or an acyl residue of a polyhydric carboxylic acid having 2 to 20 carbon atoms (provided that at least one of R ¹ represents a hydrogen atom, R ² represents a substituent other than a hydrogen atom), AO represents an oxyalkylene group having 2 to 18 carbon atoms,
m is a number from 1 to 200, n is a number from 1 to 20, and m and n satisfy the relationship m×n=1 to 200; The oxyalkylene group having 2 carbon atoms accounts for 50 mol% or more. )

[2] The additive for hydraulic compositions according to [1] above, wherein AO in the general formula (1) is an oxyalkylene group having 2 to 4 carbon atoms.

[3] The additive for hydraulic compositions according to [1] or [2], wherein AO in the general formula (1) is an oxyalkylene group having 2 to 3 carbon atoms.

[4] n in the general formula (1) is a number from 1 to 6, and m and n satisfy the relationship m x n = 1 to 150, [1] ] to [3]. The additive for hydraulic compositions according to any one of [3].

[5] R ² in the general formula (1) is a hydrogen atom, an acyl residue of rosin, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyl group having 3 to 6 carbon atoms. The additive for a hydraulic composition according to any one of [1] to [4] above, which is a residue obtained by removing a hydroxyl group from a polyhydric alcohol.

[6] The additive for a hydraulic composition according to any one of [1] to [5] above, wherein the rosin is a natural rosin.

[7] The additive for a hydraulic composition according to [6] above, wherein the natural rosin is gum rosin.

[8] For the hydraulic composition according to any one of [1] to [7] above, wherein the AO in the general formula (1) contains 90 mol% or more of an oxyalkylene group having 2 carbon atoms. Additive.

[9] The hydraulic composition according to any one of [1] to [8] above, wherein m and n in the general formula (1) are numbers that satisfy the relationship m x n = 10 to 100. Additives for things.

According to the additive for hydraulic compositions of the present invention, it is possible to improve the pumpability during pumping with a concrete pump, and a high effect can be obtained with a small amount (i.e., the pumpability can be improved with a small amount added). ), and also has the effect of not affecting the slump and air content of the hydraulic composition.

Embodiments of the present invention will be described below. However, the present invention is not limited to the following embodiments. Therefore, it should be understood that changes, improvements, etc. can be made to the following embodiments as appropriate based on the common knowledge of those skilled in the art without departing from the spirit of the present invention. In the following Examples and the like, unless otherwise specified, % means % by mass, and parts mean parts by mass.

The additive for hydraulic compositions of the present invention contains a compound represented by the following general formula (1). This compound is also called rosin polyoxyalkylene adduct.

R ¹ in general formula (1) is an acyl residue of rosin or a hydrogen atom. Here, rosin refers to a diterpene acid compound called resin acid (rosin acid). Examples of such rosin include natural rosin, modified rosin, and polymerized rosin.

Natural rosin is a mixture of resin acids present in the residue obtained by distilling off volatile substances such as essential oils from resin oil obtained from Pinaceae plants, and is classified into gum rosin, wood rosin, and tall oil rosin depending on the manufacturing method. be done.

Gum rosin is obtained by making a cut in a pine tree, filtering and purifying the raw pine resin that flows from the cut, and removing the turpentine oil by steam distillation. Wood rosin is obtained by solvent extraction of pine stump chips. Tall oil rosin is obtained by distilling and refining crude tall oil, which is a by-product in the process of producing pulp from pine wood using the kraft pulp method.

Rosin contains abietic acid as the main resin acid, and other resin acids include neoabietic acid, dehydroabietic acid, tetrahydroabietic acid, parastric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, and levopimaric acid. Contains acids, etc.

Modified rosin refers to natural rosin that has been modified.For example, natural rosin is hydrogenated under high pressure using a noble metal catalyst such as a nickel catalyst, platinum catalyst, or palladium catalyst to remove double bonds within the molecule. Examples include hydrogenated rosin in which rosin has been eliminated or reduced, and disproportionated rosin in which unstable conjugated double bonds within the molecule have been eliminated by heating natural rosin at high temperature in the presence of a noble metal catalyst or a halogen catalyst.

Polymerized rosin is a product obtained by reacting natural rosin or modified rosin with each other, and refers to dimerized products and trimerized products thereof.

Note that natural rosin is preferable as such rosin from the viewpoint of easy availability. More preferably, such natural rosin is gum rosin. Rosin is generally treated as a mixture of various compounds, and the amount of carboxylic acid is quantified by measuring the acid value. The acid value is determined by measuring according to Japanese Industrial Standards JIS K 0070.

In general formula (1), AO is an oxyalkylene group having 2 to 18 carbon atoms. Examples of the oxyalkylene group having 2 to 18 carbon atoms include oxyethylene group, oxypropylene group, oxybutylene group, oxytetramethylene group, oxystyrene group, oxidedecylene group, oxytetradecylene group, and oxyhexadecylene group. group, oxyoctadecylene group, and the like. Among these, oxyalkylene groups having 2 to 4 carbon atoms such as oxyethylene group, oxypropylene group, oxybutylene group, and oxytetramethylene group are preferred, and oxyalkylene groups having 2 to 3 carbon atoms such as oxyethylene group and oxypropylene group groups are more preferred. In addition, AO may be one type or two or more types, and in the case of two or more types, the oxyalkylene group may be in any form of a random adduct, a block adduct, or an alternating adduct.

In general formula (1), m represents the average number of moles added, m is a number from 1 to 200, preferably a number from 1 to 150, and more preferably a number from 5 to 150. , more preferably a number from 10 to 100. Further, n represents the number of moles added and is a number from 1 to 20, preferably a number from 1 to 6. Furthermore, at the same time, m and n are numbers that satisfy the relationship m×n=1 to 200, preferably numbers that satisfy the relationship m×n=1 to 150, and more preferably, m×n= It is a number that satisfies the relationship between 10 and 100. When the product of m and n exceeds 200, the manufacturing cost becomes too high and the viscosity of the hydraulic composition becomes too high. Moreover, when the product of m and n is less than 1, the amount of air in the resulting hydraulic composition becomes excessive.

In addition, in order to obtain excellent pumpability, in general formula (1), it is necessary that the oxyalkylene group having 2 carbon atoms in AO accounts for 50 mol% or more, preferably 80 mol% or more. and more preferably 90 mol% or more. If the content of oxyalkylene groups having 2 carbon atoms in AO is less than 50 mol %, sufficient pumpability cannot be obtained.

In general formula (1), when n is 1, R ¹ is an acyl residue of rosin. When n is 2 or more, at least one of R ¹ is an acyl residue of rosin.

In the general formula (1), R ² is a hydrogen atom, an acyl residue of rosin, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a hydroxyl group from a polyhydric alcohol having 3 to 20 carbon atoms. The removed residue is an acyl group having 1 to 20 carbon atoms or an acyl residue of a carboxylic acid having 2 to 20 carbon atoms. However, when at least one of R ¹ represents a hydrogen atom, R ² is a substituent other than a hydrogen atom.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-hexyl group, n-octyl group, Straight chain or branched alkyl groups such as a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icosyl group are mentioned. Among these, alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group are preferred.

Examples of the alkenyl group having 2 to 20 carbon atoms include ethenyl group, n-propenyl group, n-butenyl group, n-pentenyl group, n-hexenyl group, n-heptenyl group, n-octenyl group, n-nonel group. , n-decenyl group, n-undecenyl group, n-dodecenyl group, n-tridecenyl group, n-tetradecenyl group, n-pentadecenyl group, n-hexadecenyl group, n-heptadecenyl group, n-octadecenyl group, n-nonadecenyl group , n-icosenyl group, and the like. Among these, alkenyl groups having 2 to 5 carbon atoms such as ethenyl group, n-propenyl group, n-butenyl group, and n-pentenyl group are preferred.

Examples of residues obtained by removing hydroxyl groups from polyhydric alcohols having 3 to 20 carbon atoms include residues obtained by removing hydroxyl groups from polyhydric alcohols having 3 to 20 carbon atoms, such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sorbitan. Examples include groups. Among these, residues obtained by removing hydroxyl groups from polyhydric alcohols having 3 to 6 carbon atoms, such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sorbitan, are preferred.

Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, undecanoyl group, and dodecanoyl group. group, tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group, nonadecanoyl group, icosanoyl group, 2-ethylhexanoyl group, 3-ethylheptanoyl group, 3- Examples include straight chain or branched acyl groups such as ethyldecanoyl group.

Examples of acyl residues of polyvalent carboxylic acids having 2 to 20 carbon atoms include oxalic acid, malonic acid, dipropylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, glutaric acid, 2-methylglutaric acid, 2,2-dimethylglutaric acid, 2,4-dimethylglutaric acid, 3-methylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, 3-methyladipic acid, pimeline Acid, 2,2,6,6-tetramethylpimelic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, pentadecanedioic acid, tetradecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, Acyl residue obtained by removing the hydroxyl group from an aliphatic polycarboxylic acid having 2 to 20 carbon atoms such as eicosandioic acid and 1,4-cyclohexanedicarboxylic acid, cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid , acyl residue obtained by removing the hydroxyl group from an alicyclic polycarboxylic acid having 6 to 20 carbon atoms such as dicyclohexyl-4,4'-dicarboxylic acid and camphoric acid, terephthalic acid, isophthalic acid, 2-methylterephthalic acid, 4 , 4'-stilbene dicarboxylic acid, naphthalene dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, orthophthalic acid, diphenoxyethane dicarboxylic acid, diphenyl ether dicarboxylic acid, and diphenyl sulfone dicarboxylic acid. An example is an acyl residue obtained by removing a hydroxyl group from a carboxylic acid. These acyl residues may be linear or branched.

The method for producing the compound represented by general formula (1) is not particularly limited. For example, by using a catalyst etc. in rosin which is a mixture of resin acids such as abietic acid, neoabietic acid, dehydroabietic acid, tetrahydroabietic acid, parastric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, and levopimaric acid. A method of producing a rosin polyoxyalkylene adduct represented by the general formula (1) by adding alkylene oxide by a conventional method, or a method of adding alkylene oxide by a conventional method by using a catalyst etc. to R ² in advance. , followed by esterification with rosin to produce a rosin polyoxyalkylene adduct represented by general formula (1).

The additive for hydraulic compositions according to the present invention is used in hydraulic compositions containing hydraulic binders used in civil engineering, construction, and the like.

The additive for hydraulic compositions according to the present invention is used in combination with existing dispersants. Examples of such dispersants include ligninsulfonic acid dispersants, polycarboxylic acid dispersants, naphthalenesulfonic acid dispersants, aminosulfonic acid dispersants, and the like. In particular, from the viewpoint of ensuring dispersion retention, the present invention contains at least one dispersant selected from the group consisting of a ligninsulfonic acid dispersant and a polycarboxylic acid dispersant.

The additive for hydraulic compositions according to the present invention can be used in combination with existing admixtures, so long as it does not impair pumpability or affect slump and air content. Examples of such admixtures include air-entraining water reducers, high-performance air-entraining water reducers, air-entraining agents, defoamers, shrinkage reducing agents, thickeners, hardening accelerators, etc.

Hydraulic binders used in the preparation of hydraulic compositions to which the additive for hydraulic compositions according to the present invention can be used include, for example, various Portland cements such as ordinary Portland cement, early-strength Portland cement, and medium-heat Portland cement. In addition to cement, there are various mixed cements such as blast furnace cement, fly ash cement, and silica fume cement. Further, various admixtures such as pulverized blast furnace slag powder, fly ash, and silica fume may be used in combination with the various cements listed above.

Further, when aggregate is used for preparing the hydraulic composition, examples of the aggregate include fine aggregate and coarse aggregate. Examples of the fine aggregate include river sand, mountain sand, sea sand, crushed sand, and slag fine aggregate, and examples of the coarse aggregate include river gravel, crushed stone, lightweight aggregate, and the like.

Furthermore, the water binder ratio of the hydraulic composition is not particularly limited. Highly effective at commonly used water binder ratios.

The additive for hydraulic compositions according to the present invention is mixed in a ratio of 0.00001 to 0.1 parts by mass, and preferably 0.0005 to 0.1 parts by mass, per 100 parts by mass of hydraulic binder.

Examples will be given below to make the structure and effects of the present invention more specific, but the present invention is not limited to these Examples. In the Examples and Comparative Examples below, unless otherwise specified, "part" means part by mass, and "%" means % by mass.

Test Category 1 (Synthesis of compound represented by general formula (1))
-Synthesis of Compound (A-1) In a 2L stainless steel pressure-resistant container, 626.5 g of "gum rosin" X grade (acid value: 171 mgKOH/g) produced in the People's Republic of China (hereinafter simply referred to as "produced in China") was added. 9 g of potassium hydroxide and 2.0 g of potassium hydroxide were charged, heated to 120° C., and dehydrated under reduced pressure for 1 hour with stirring. The pressure was returned to normal with nitrogen, and then 1264 g of ethylene oxide was injected under pressure of 0.4 MPa at 150 to 160° C., and then 107 g of propylene oxide was injected under the same conditions, and the mixture was aged at that temperature for 1 hour. Thereafter, it was cooled, 20g of adsorbent (trade name: Kyoward 600, manufactured by Kyowa Kagaku Kogyo Co., Ltd.) was added, and after vacuum dehydration at 120°C, pressure filtration was performed to obtain compound (A-1). .

・Synthesis of compound (A-2) In a 2L stainless steel pressure-resistant container, 541.7g of "Gum Rosin" X grade (acid value: 171mgKOH/g) from China and 2.0g of potassium hydroxide were charged. The mixture was heated to .degree. C. and dehydrated under reduced pressure for 1 hour while stirring. The pressure was returned to normal with nitrogen, and then 1456 g of ethylene oxide was injected under pressure of 0.4 MPa at 150 to 160° C., and the mixture was aged at that temperature for 1 hour. After cooling, 2.7 g of 85% phosphoric acid was added, and after vacuum dehydration at 120° C., pressure filtration was performed to obtain compound (A-2).

・Synthesis of compound (A-3) In a 2L stainless steel pressure-resistant container, 191.9g of "Gum Rosin" X grade (acid value: 171mgKOH/g) from China and 2.0g of potassium hydroxide were charged. The mixture was heated to .degree. C. and dehydrated under reduced pressure for 1 hour while stirring. The pressure was returned to normal with nitrogen, and then 1806 g of ethylene oxide was injected under pressure of 0.4 MPa at 150 to 160° C., and the mixture was aged at that temperature for 1 hour. After cooling, the mixture was collected to obtain compound (A-3).

・Synthesis of compound (A-4) In a 1 L glass reaction vessel, 500.0 g of α-methoxy-ω-hydroxy-poly(n=45)oxyethylene and X grade (acid value) of “gum rosin” from China were added. :171mgKOH/g) and 7.2g of methanesulfonic acid were charged, and after purging with nitrogen, dehydration was performed under reduced pressure at 150°C and 0.5kPa to perform an esterification reaction. The reaction was terminated when the esterification rate reached 99% or more, and compound (A-4) was obtained by purification.

・Synthesis of compound (A-5) In a 1L glass reaction vessel, 92.1g of glycerin as a reagent, 656.2g of X grade (acid value: 171mgKOH/g) of "Gum Rosin" produced in China, and 19% of methanesulfonic acid were added. After charging 2 g and purging with nitrogen, dehydration was performed under reduced pressure at 150° C. and 0.5 kPa to perform an esterification reaction. The reaction was terminated when the esterification rate reached 99% or more, and the mixture was purified to obtain Compound (A-5).

-Synthesis of Compound (A-6) In a 1L glass reaction vessel, 93.6g of sorbitol as a reagent, 656.2g of "Gum Rosin" X grade (acid value: 171mgKOH/g) from China, and 19% of methanesulfonic acid were added. After charging 2 g and purging with nitrogen, dehydration was performed under reduced pressure at 150° C. and 0.5 kPa to perform an esterification reaction. The reaction was terminated when the esterification rate reached 99% or more, and compound (A-6) was obtained by purification.

・Synthesis of compound (A-7) In a 1 L glass reaction vessel, 309.8 g of poly(n=70) ethylene glycol and 52.5 g of X grade (acid value: 171 mgKOH/g) of "Gum Rosin" from China were added. 5.8 g of para-toluenesulfonic acid monohydrate was charged, and after purging with nitrogen, dehydration was performed under reduced pressure at 150° C. and 0.5 kPa to perform an esterification reaction. The reaction was terminated when the esterification rate reached 99% or more, and the mixture was purified to obtain compound (A-7).

・Synthesis of compound (A-8) In a 1 L glass reaction vessel, 500.0 g of α-methallyl-ω-hydroxy-poly(n=50)oxyethylene and X grade of “gum rosin” from China (acid value: 171 mg KOH /g) and 12.7 g of p-toluenesulfonic acid monohydrate were charged, and after purging with nitrogen, dehydration was performed under reduced pressure at 150° C. and 0.5 kPa to perform an esterification reaction. The reaction was terminated when the esterification rate reached 99% or more, and the mixture was purified to obtain compound (A-8).

- Synthesis of Compound (A-9) Compound (A-9) was obtained by performing the same synthesis as Compound (A-1), except that the amount of raw materials charged was changed as shown in Table 1.

The contents of compounds (A-1) to (A-9) and (R-1) to (R-2) synthesized above are summarized in Table 1.

In Table 1, R-1 and R-2 are shown below. R-1 and R-2 are used as they are.
R-1: X grade of "gum rosin" from China R-2: Reagent polyethylene glycol (molecular weight 1000)

^R1 in Table 1 is shown below.
"Gum rosin acyl residue": A product obtained by removing the hydroxyl group from the carboxylic acid of gum rosin "Gum rosin acyl residue: H = 2:1": The molar ratio of gum rosin acyl residue and hydrogen atom in ^R1 is 2:1
"Gum rosin acyl residue: H = 4:1": The molar ratio of gum rosin acyl residue and hydrogen atom in ^R1 is 4:1
EO: Oxyethylene group PO: Oxypropylene group

Test category 2 (preparation of concrete composition)
・Examples 1 to 13 and Comparative Examples 1 to 6
Using a forced twin-screw mixer with a capacity of 60 liters, each concrete composition listed in Table 3 was prepared by mixing for 90 seconds with the contents listed in Table 2. Note that for each concrete composition, the target air content was 4.5±1.5% and the target slump was 18±1 cm. In Example 13 and Comparative Example 6, kneading was carried out in the same manner using a forced twin-screw mixer with a capacity of 2.0 m ³ . Note that the temperature of the concrete composition was 20°C.

In Table 2, each formulation is shown below.

・Blend No. 1
Cement: Ordinary Portland cement (density = 3.16g/cm ³ )
Fine aggregate 1: Land sand (surface dry density = 2.58 g/cm ³ )
Coarse aggregate 1: Crushed stone 2005 (surface dry density = 2.66 g/cm ³ )

In formulation No. 1, the following compounds were further used.
Water reducing agent: AE water reducing agent standard type I type (high performance type) Chewpol EX60 (manufactured by Takemoto Yushi Co., Ltd., a composite of modified lignin sulfonic acid compound and polycarboxylic acid compound) used at 1.0% based on the cement mass Antifoaming agent: AFK-2 (manufactured by Takemoto Yushi Co., Ltd.) used at 0.0005% based on the cement mass AE agent: AE-300 (manufactured by Takemoto Yushi Co., Ltd.) used at 0.0015% based on the cement mass

・Combination No.2
Cement: Ordinary Portland cement (density = 3.16g/cm ³ )
BFS (ground blast furnace slag powder): Ground blast furnace slag powder 4000 brane (density = 2.89 g/cm ³ )
FA (fly ash): Fly ash type II (density = 2.21 g/cm ³ )
Fine aggregate 1: Land sand (surface dry density = 2.57 g/cm ³ )
Coarse aggregate 1: Crushed stone 2005 (surface dry density = 2.68 g/cm ³ )

In formulation No. 2, the following compounds were further used.
Water reducing agent: High performance AE water reducing agent standard type I type (high performance type) Chewpol HP-8 (manufactured by Takemoto Yushi Co., Ltd., polycarboxylic acid copolymer) used at 0.7% based on the cement mass Antifoaming agent: AFK- 2 (manufactured by Takemoto Yushi Co., Ltd.) at 0.0003% based on the mass of cement.
AE agent: AE-200 (manufactured by Takemoto Yushi Co., Ltd.) at 0.0002% based on the cement mass

・Combination No.3
Cement: Ordinary Portland cement (density = 3.16g/cm ³ )
Fine aggregate 1: Mountain sand (surface dry density = 2.57 g/cm ³ )
Fine aggregate 2: Crushed sand (surface dry density = 2.74 g/cm ³ )
Coarse aggregate 1: Crushed stone 2005 (surface dry density = 2.75 g/cm ³ )
Coarse aggregate 2: Crushed stone 2005 (surface dry density = 2.71 g/cm ³ )

In formulation No. 3, the following compounds were further used.
Water reducing agent: AE water reducing agent delayed type I type (high performance type) Sikament JR (manufactured by Nippon Sika Co., Ltd., modified polycarboxylic acid polyether polymer and modified polyol) at 1.3% based on the cement mass
Antifoaming agent: AFK-2 (manufactured by Takemoto Yushi Co., Ltd.) at 0.0005% based on the cement mass
AE agent: Master Air 202 (manufactured by BASF Japan, modified rosin acid compound-based anionic surfactant) at 0.005% based on cement mass

Test Category 3 (Test and evaluation of concrete composition)
For each concrete composition prepared, the air content, slump, and O funnel flow time were measured as described below, and the results are summarized in Table 3. In addition, in Example 13 and Comparative Example 6, the pump pressure was also measured.

Addition rate The mass % of each compound relative to the total mass of the hydraulic binder is shown. Each compound was used as a part of the mixing water.
Air volume (volume%):
The measurement was performed in accordance with Japanese Industrial Standard JIS A 1128.
Slump (cm):
At the same time as measuring the air volume, measurements were also made in accordance with Japanese Industrial Standard JIS A 1101.
・O funnel flow time (sec)
It was measured after slump measurement in accordance with the Japan Society of Civil Engineers standard JSCE-F512-2018. It was determined that the smaller the O funnel flow time, the better the pumpability.
Pump pressure (MPa)
Using a concrete pump truck "PH50B-17 (Kyokuto Kaihatsu Co., Ltd.)", the maximum pressure gauge reading at a flow rate of 20 m ³ /hour was read and recorded, and this was taken as the concrete pumping pressure (MPa).

(result)
As is clear from the results shown in Examples 1 to 13 in Table 3, the present invention improves the pumpability of the hydraulic composition obtained, and the hydraulic composition has a small effect on slump and air volume. It was confirmed that it is possible to provide additives for In addition, in Example 13, when compared with the condition of Comparative Example 6 without additives, the pumping pressure at the time of discharge of 20 m ³ / hour was reduced, and it was confirmed that the pumping performance was actually improved. .

On the other hand, it was confirmed that in Comparative Examples 1, 4, and 6 in which no additives for hydraulic compositions were blended, it was not possible to reduce the O funnel flow time. Moreover, in Comparative Examples 2 and 5, a so-called AE agent, which is a compound having no oxyalkylene group, was used, and due to its effect, although the pumpability was good, the amount of air increased. Furthermore, in Comparative Example 3, polyethylene glycol was used as the compound, and in this case, it was confirmed that the O funnel flow time could not be reduced.

The additive for hydraulic compositions of the present invention can be used as an additive when preparing hydraulic compositions.

Claims (9)

It is added to a hydraulic composition containing a hydraulic binder and is blended in a proportion of 0.00001 to 0.1 part by mass per 100 parts by mass of the hydraulic binder,
Contains a compound represented by the following general formula (1) and a dispersant,
A hydraulic composition in which the dispersant is at least one selected from the group consisting of a lignin sulfonic acid-based dispersant and a polycarboxylic acid-based dispersant, and is used to improve pumpability of the hydraulic composition. Additives for use.

(However, in general formula (1), R ¹ represents an acyl residue of rosin or a hydrogen atom (however, when n is 1, R ¹ represents an acyl residue of rosin, and when n is 2 or more) , at least one of R ¹ represents an acyl residue of rosin), R ² is a hydrogen atom, an acyl residue of rosin, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, Represents a residue obtained by removing a hydroxyl group from a polyhydric alcohol having 3 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, or an acyl residue of a polyhydric carboxylic acid having 2 to 20 carbon atoms (provided that at least one of R ¹ represents a hydrogen atom, R ² represents a substituent other than a hydrogen atom), AO represents an oxyalkylene group having 2 to 18 carbon atoms,
m is a number from 1 to 200, n is a number from 1 to 20, and m and n satisfy the relationship m×n=1 to 200; The oxyalkylene group having 2 carbon atoms accounts for 50 mol% or more. ) The additive for hydraulic compositions according to claim 1, wherein AO in the general formula (1) is an oxyalkylene group having 2 to 4 carbon atoms. The additive for hydraulic compositions according to claim 1 or 2, wherein AO in the general formula (1) is an oxyalkylene group having 2 to 3 carbon atoms. The method according to claims 1 to 3, wherein n in the general formula (1) is a number from 1 to 6, and the m and n satisfy the relationship of m×n=1 to 150. The additive for hydraulic compositions according to any one of the items. R ² in the general formula (1) is a hydrogen atom, an acyl residue of rosin, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a polyhydric alcohol having 3 to 6 carbon atoms. The additive for hydraulic compositions according to any one of claims 1 to 4, which is a residue obtained by removing a hydroxyl group from. The additive for a hydraulic composition according to any one of claims 1 to 5, wherein the rosin is a natural rosin. The additive for hydraulic compositions according to claim 6, wherein the natural rosin is gum rosin. The additive for a hydraulic composition according to any one of claims 1 to 7, wherein in the AO in the general formula (1), oxyalkylene groups having 2 carbon atoms account for 90 mol% or more. The additive for hydraulic compositions according to any one of claims 1 to 8, wherein m and n in the general formula (1) are numbers satisfying the relationship m x n = 10 to 100. .