JP6616557B1 - Bleeding inhibitor - Google Patents

Abstract

There is provided a bleeding inhibitor capable of obtaining a hydraulic composition with suppressed bleeding. A bleeding inhibitor used in a hydraulic binder containing cement and a hydraulic composition containing water, the bleeding inhibitor comprising a predetermined polyoxyalkylene compound.

Description

  The present invention relates to a bleeding inhibitor. More specifically, the present invention relates to a bleeding inhibitor capable of obtaining a hydraulic composition with suppressed bleeding.

  Conventionally, hydraulic compositions have been widely used as cement compositions such as cement paste, mortar, and concrete. This hydraulic composition has a problem that floating water (bleeding) is generated between adding water and kneading to curing.

  If a large amount of this bleeding occurs after the placement of the hydraulic composition, the water passage that occurs when the water in the hydraulic composition comes to the surface deteriorates the compactness of the hydraulic composition structure and decreases the strength during curing. There is a bug that causes

  Therefore, in order to prevent this problem, various additives for hydraulic compositions are used, and among them, for example, polyethylene glycol is also used (see Patent Document 1).

JP-A-6-64956

  However, the bleeding tends to increase due to the deterioration of the aggregate situation. Specifically, high-quality river sand / mountain sand, river gravel / mountain gravel, etc. have been used as aggregates in the past, but recently, high-quality aggregates are difficult to collect, and crushed stone and crushed sand are used as aggregates. There is a need. In this case, in order to obtain the same workability as when the conventional aggregate is used, it is necessary to increase the unit water amount, but the bleeding tends to increase by increasing the unit water amount. And it was difficult for polyethylene glycol as described in Patent Document 1 to sufficiently suppress and reduce bleeding. Therefore, there is a need for a bleeding inhibitor that is unlikely to affect other properties of the hydraulic composition and can sufficiently suppress bleeding.

  The present invention has been made in view of such problems of the prior art, and an object of the present invention is to provide a bleeding inhibitor capable of obtaining a hydraulic composition in which bleeding is suppressed. It is.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific compound as a bleeding inhibitor.

  According to the present invention, the following bleeding inhibitor is provided.

[1] A bleeding inhibitor used for a hydraulic binder containing cement and a hydraulic composition containing water,
A bleeding inhibitor comprising a polyoxyalkylene compound represented by the following formula (1).

Ｒ^１：炭素数６〜２５の芳香族炭化水素基及びフェノール性の２個の水酸基を有する化合物から全ての水酸基を除いた残基
Ｘ，Ｙ：それぞれ独立に、水素原子又は炭素数１〜２２のアルキル基
ＯＲ^２，Ｒ^３Ｏ：それぞれ独立に、炭素数２〜４のオキシアルキレン基
ｍ，ｎ：１〜２９９の整数であって、且つｍ＋ｎ＝６０〜３００を満足する整数

R ¹ : a residue obtained by removing all hydroxyl groups from a compound having an aromatic hydrocarbon group having 6 to 25 carbon atoms and two phenolic hydroxyl groups X and Y: each independently a hydrogen atom or 1 to 22 carbon atoms Alkyl group OR ² , R ³ O: each independently an oxyalkylene group having 2 to 4 carbon atoms m, n: an integer having 1 to 299 and satisfying m + n = 60 to 300

[2] The bleeding inhibitor according to the above [1], wherein in the formula (1), R ¹ is a group having a bis (4-hydroxyphenyl) skeleton represented by the following formula (2).

但し、式（２）において、Ｚは、炭素数１〜１３の直鎖状または分岐状のアルキレン基、或いは、スルホニル基である。

However, in Formula (2), Z is a C1-C13 linear or branched alkylene group or a sulfonyl group.

[3] In the formula (1), R ¹ is a group selected from 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, or bis (4-hydroxyphenyl) sulfone. The bleeding inhibitor according to [1] or [2], which is a residue excluding a hydroxyl group.

[4] The bleeding inhibitor according to any one of [1] to [3], wherein in the formula (1), X and Y are hydrogen atoms.

[5] In the formula (1), bleeding suppression according to any one of the above [1] to [4], wherein 90 mol% or more of all oxyalkylene groups of OR ² and R ³ O is an oxyethylene group. Agent.

[6] In any one of [1] to [5], in the formula (1), m and n are each an integer of 1 to 219, and m + n is an integer satisfying 70 to 220. Bleeding inhibitor.

  The bleeding inhibitor of the present invention has an effect that a hydraulic composition in which bleeding is suppressed can be obtained.

  Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments, and based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. It should be understood that modifications, improvements, and the like appropriately added to the embodiments described above fall within the scope of the present invention.

[1] Bleeding inhibitor:
The present invention is a bleeding inhibitor for use in a hydraulic binder containing cement and a hydraulic composition containing water, the bleeding inhibitor containing a polyoxyalkylene compound represented by the following formula (1). is there.

Ｒ^１：炭素数６〜２５の芳香族炭化水素基及びフェノール性の２個の水酸基を有する化合物から全ての水酸基を除いた残基
Ｘ，Ｙ：それぞれ独立に、水素原子又は炭素数１〜２２のアルキル基
ＯＲ^２，Ｒ^３Ｏ：それぞれ独立に、炭素数２〜４のオキシアルキレン基
ｍ，ｎ：１〜２９９の整数であって、且つｍ＋ｎ＝６０〜３００を満足する整数

R ¹ : a residue obtained by removing all hydroxyl groups from a compound having an aromatic hydrocarbon group having 6 to 25 carbon atoms and two phenolic hydroxyl groups X and Y: each independently a hydrogen atom or 1 to 22 carbon atoms Alkyl group OR ² , R ³ O: each independently an oxyalkylene group having 2 to 4 carbon atoms m, n: an integer having 1 to 299 and satisfying m + n = 60 to 300

[1-1] Polyoxyalkylene compound represented by formula (1):
In the bleeding inhibitor of the present invention, R ¹ in the polyoxyalkylene compound represented by the formula (1) is, for example, hydroquinone, catechol, binaphthol, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl). Propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxyphenyl) butane, bis (4 -Hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone, 5,5 '-(1-methylethylidene) -bis [1,1'-(bisphenyl) -2-ol] propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclohexane Examples thereof include a residue obtained by removing a hydroxyl group from xane. R ¹ may be a group (residue) having a bis (4-hydroxyphenyl) skeleton represented by the following formula (2). Among these, a residue obtained by removing two hydroxyl groups from 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, and bis (4-hydroxyphenyl) sulfone is preferable. . With these residues, an excellent bleeding suppression effect is exhibited.

式（２）において、Ｚは、炭素数１〜１３の直鎖状または分岐状のアルキレン基、或いは、スルホニル基である。

In Formula (2), Z is a C1-C13 linear or branched alkylene group or a sulfonyl group.

  As X in Formula (1), a hydrogen atom or a C1-C22 alkyl group is mentioned. Examples of the alkyl group having 1 to 22 carbon atoms include methyl group, ethyl group, butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group. Group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group, 2-methyl-pentyl group, 2-ethyl-hexyl group, 2-propyl-heptyl group, 2-butyl-octyl group, 2- Examples include pentyl-nonyl group, 2-hexyl-decyl group, 2-heptyl-undecyl group, 2-octyl-dodecyl group, 2-nonyl-tridecyl group and the like. Among these, as X, a hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable.

  Moreover, about Y in Formula (1), the same thing as X can be mentioned.

  Here, it is preferable that X and Y are hydrogen atoms from the viewpoints of ease of synthesis of the compound, availability of raw materials, and economical efficiency.

In the formula (1), OR ² represents an oxyalkylene group having 2 to 4 carbon atoms. When a plurality of OR ² are present, two or more types of oxyalkylene groups may be used. Specifically, OR ² preferably contains an oxyethylene group and / or an oxypropylene group, more preferably contains 50 mol% or more of oxyethylene groups, and more preferably 90 mol% of oxyethylene groups. It contains above. In addition, when two or more types of oxyalkylene groups are added, the order of bonding is not particularly limited, and random bonding or block bonding may be used.

Further, R ³ O in the formula (1) is the same as described for OR ² .

In OR ² and R ³ O, it is preferable that 90 mol% or more of all oxyalkylene groups obtained by summing OR ² and R ³ O are oxyethylene groups. Good bleeding suppression effect.

  In the formula (1), m and n represent the number of added moles of the polyoxyalkylene group, and m + n represents the total number of added moles of the polyoxyalkylene group. m and n are each an integer of 1 to 299, preferably an integer of 1 to 219. Further, m + n is 60 ≦ m + n ≦ 300, and preferably 70 ≦ m + n ≦ 220. When m + n is smaller than 60, the bleeding reduction effect is not exhibited. If m + n is too large, the manufacturing cost is high and it is not realistic.

  It does not specifically limit as a manufacturing method of the polyoxyalkylene compound whose X and Y in Formula (1) are a hydrogen atom, It can manufacture with a well-known manufacturing method.

For example, it can be obtained by adding alkylene oxide to a compound having two phenolic hydroxyl groups as R ¹ . A catalyst can be used when adding an alkylene oxide. As a catalyst for addition polymerization of alkylene oxide, alkali catalysts such as alkali metals and alkaline earth metals, their hydroxides, alcoholates, Lewis acid catalysts, and composite metal catalysts can be used. is there.

  Examples of the alkali catalyst include sodium, potassium, sodium potassium amalgam, sodium hydroxide, potassium hydroxide, sodium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium butoxide and the like. . Sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, and potassium butoxide are preferable.

  Examples of the Lewis acid catalyst include tin tetrachloride, boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride di-n-butyl ether complex, boron trifluoride tetrahydrofuran complex, boron trifluoride phenol complex, three Examples thereof include boron trifluoride compounds such as a boron fluoride acetic acid complex.

  The bleeding inhibitor of the present invention is not limited to a solution and may be a solid.

  The bleeding inhibitor of the present invention may be the polyoxyalkylene compound itself represented by the formula (1), but it is preferable to add an antioxidant.

  In addition, the bleeding reducing agent of the present invention may be used in combination with a conventionally known additive for hydraulic compositions or may be mixed.

  Here, the bleeding inhibitor of the present invention is used by blending with a hydraulic binder containing cement and a hydraulic composition containing water.

  The hydraulic binder contains cement. Examples of the cement include various mixed cements such as blast furnace cement, fly ash cement, and silica fume cement, in addition to various portland cements such as ordinary portland cement, early-strength portland cement, and moderately heated cement.

  In order to obtain an effect as a bleeding reducing agent, the addition amount is preferably 0.01 to 3.0 parts by mass, more preferably 0.01 to 1.0 part by mass with respect to 100 parts by mass of the hydraulic binder. 0.02-0.5 part by mass is more preferable.

  Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following examples and comparative examples, “part” means “part by mass”, “%” means “mass%”, and “ppm” means mass ppm.

Example 1
-Production of bleeding inhibitor (EX-1) In a pressure vessel equipped with a stirrer, a pressure gauge, and a thermometer, "New Pole BPE-60 (manufactured by Sanyo Chemical Co., Ltd., 2,2-bis (4-hydroxyphenyl)" All hydroxyl groups of propane were charged with 257.3 g of a total of 6 mol of ethylene oxide adduct) ”and 1.5 g of potassium hydroxide. Subsequently, after raising the temperature of the reaction system to 120 ° C., the system was dehydrated for 1 hour under reduced pressure. Thereafter, 1242.7 g of ethylene oxide (indicated as “EO” in Table 1) was added to the reaction system at a gauge pressure of 0.4 MPa over 5 hours while maintaining the temperature at 130 ± 5 ° C. Thereafter, the reaction temperature (130 ± 5 ° C.) was maintained for 1 hour. Then, after neutralizing using "KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.)" and performing filtration, 2,6-di-tert-butyl-4-methylphenol (in Table 1, 200 ppm was added to the filtered collected product to obtain a bleeding inhibitor (EX-1) containing a polyoxyalkylene compound represented by the formula (1).

Example 2
-Production of bleeding inhibitor (EX-2) In a pressure vessel equipped with a stirrer, a pressure gauge, and a thermometer, "New Pole BPE-60 (manufactured by Sanyo Chemical Co., Ltd., 2,2-bis (4-hydroxyphenyl)" All the hydroxyl groups of propane were charged with 318.9 g of a total of 6 mol of ethylene oxide adduct) ”and 3.0 g of potassium hydroxide. Subsequently, after raising the temperature of the reaction system to 120 ° C., the system was dehydrated for 1 hour under reduced pressure. Thereafter, 2681.1 g of ethylene oxide was added to the reaction system over 6 hours at a gauge pressure of 0.4 MPa while maintaining at 130 ± 5 ° C. Then, it hold | maintained at reaction temperature (130 +/- 5 degreeC) for 1 hour, Then, it collect | recovered and obtained the bleeding inhibitor (EX-2) which consists of a polyoxyalkylene compound shown by Formula (1).

Example 3
-Production of bleeding inhibitor (EX-3) In a pressure vessel equipped with a stirrer, a pressure gauge, and a thermometer, "New Pole BPE-60 (manufactured by Sanyo Chemical Co., Ltd., 2,2-bis (4-hydroxyphenyl)" All the hydroxyl groups of propane were charged with 338.5 g of a total of 6 mol of ethylene oxide adduct) ”and 10.0 g of tert-butoxypotassium. Subsequently, after raising the temperature of the reaction system to 120 ° C., the system was dehydrated for 1 hour under reduced pressure. Thereafter, 4661.5 g of ethylene oxide was added to the reaction system over 7 hours at a gauge pressure of 0.4 MPa while maintaining the temperature at 130 ± 5 ° C. Then, it hold | maintained at reaction temperature (130 +/- 5 degreeC) for 1 hour, and collect | recovered after that. Neutralization was performed using “KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.)”, and filtration was performed to obtain a bleeding inhibitor (EX-3) comprising a polyoxyalkylene compound represented by the formula (1).

Example 4
-Production of bleeding inhibitor (EX-4) In a pressure vessel equipped with a stirrer, a pressure gauge, and a thermometer, "New Pole BPE-60 (manufactured by Sanyo Chemical Co., Ltd., 2,2-bis (4-hydroxyphenyl)" All the hydroxyl groups of propane were charged with 272.5 g of ethylene oxide (total 6 mol adduct) ”and 5.0 g of potassium hydroxide. Subsequently, after raising the temperature of the reaction system to 130 ° C., dehydration was performed for 1 hour in the system under reduced pressure. Thereafter, 4727.5 g of ethylene oxide was added to the reaction system at a gauge pressure of 0.4 MPa over 8 hours while maintaining at 130 ± 5 ° C. Then, it hold | maintained at reaction temperature (130 +/- 5 degreeC) for 1 hour, and collect | recovered after that. Neutralized and dehydrated by adding 85% phosphoric acid (reagent made by Kishida Chemical Co., Ltd.) to pH 6, and added 1000 ppm of the antioxidant OX1 to the neutralized product, to suppress bleeding (EX-4) Got.

Example 5
-Production of bleeding inhibitor (EX-5) In a pressure vessel equipped with a stirrer, a pressure gauge, and a thermometer, 250.3 g of commercially available bis (4-hydroxyphenyl) sulfone and 8.0 g of tert-butoxy potassium were charged. It is. Subsequently, after raising the temperature of the reaction system to 120 ° C., 176 g of ethylene oxide was charged and the reaction was started. After confirming that the pressure decreased, 4224.0 g of ethylene oxide was added to the reaction system over 8 hours at a gauge pressure of 0.4 MPa while maintaining the temperature at 130 ± 5 ° C. The reaction temperature was maintained for 1 hour and then recovered. Neutralization was performed using KYOWARD 700 (manufactured by Kyowa Chemical Industry Co., Ltd.), filtration was performed, hydroquinone monomethyl ether (OX3) was added as an antioxidant to the filtered product at 150 ppm, and a bleeding inhibitor (EX-5) )

Example 6
-Production of bleeding inhibitor (EX-6) As shown in Table 1, the bleeding inhibitor (EX-6) was replaced with bis (4-hydroxyphenyl) sulfone used in Example 5 instead of bis (4-hydroxyphenyl) sulfone. This was prepared in the same manner as in Example 5 except that hydroxyphenyl) methane was used and the amount of ethylene oxide was changed.

Example 7
-Production of bleeding inhibitor (EX-7) In a pressure vessel equipped with a stirrer, a pressure gauge, and a thermometer, "New Pole BPE-60 (manufactured by Sanyo Chemical Co., Ltd., 2,2-bis (4-hydroxyphenyl)" 700.3 g of ethylene oxide total 6 mol adduct) ”and 5.5 g of potassium hydroxide were charged to all hydroxyl groups of propane. Subsequently, after raising the temperature of the reaction system to 120 ° C., the system was dehydrated for 1 hour under reduced pressure. Thereafter, 4634 g of ethylene oxide was added to the reaction system at a gauge pressure of 0.4 MPa over 5 hours while maintaining the temperature at 130 ± 5 ° C. Thereafter, the reaction temperature (130 ± 5 ° C.) was maintained for 1 hour. Further, 165 g of propylene oxide (denoted as “PO” in Table 1) was added at the same temperature, held at the reaction temperature (130 ± 5 ° C.) for 1 hour, and then recovered. Neutralization was performed using KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.), followed by filtration to obtain a bleeding inhibitor (EX-7).

Example 8
-Production of Bleeding Inhibitor (EX-8) As shown in Table 1, the bleeding inhibitor (EX-8) is composed of ethylene oxide (referred to as “EO” in Table 1) and propylene oxide (referred to as “PO” in Table 1). The production was carried out in the same manner as in Example 7 except that the amount was changed.

Example 9
-Production of bleeding inhibitor (EX-9) In a pressure vessel equipped with a stirrer, a pressure gauge, and a thermometer, "New Pole BPE-60 (manufactured by Sanyo Chemical Co., Ltd., 2,2-bis (4-hydroxyphenyl)" All the hydroxyl groups of propane were charged with 628.4 g of a total of 6 mol of ethylene oxide adduct) ”and 4.0 g of potassium hydroxide. Subsequently, after raising the temperature of the reaction system to 120 ° C., the system was dehydrated for 1 hour under reduced pressure. Thereafter, 3371.7 g of ethylene oxide was added to the reaction system over 5 hours at a gauge pressure of 0.4 MPa while maintaining the temperature at 150 ± 5 ° C. Then, it hold | maintained at reaction temperature (150 +/- 5 degreeC) for 1 hour, and collect | recovered after that. Neutralization was performed using KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.), followed by filtration to obtain a bleeding inhibitor (EX-9).

Comparative Example 1
-Production of bleeding inhibitor (RE-1) 106 g of commercially available diethylene glycol and 4.4 g of potassium hydroxide were charged into a pressure vessel equipped with a stirrer, a pressure gauge, and a thermometer. Next, the temperature of the reaction system was raised to 120 ° C. Thereafter, 4312 g of ethylene oxide was added to the reaction system over 5 hours at a gauge pressure of 0.4 MPa while maintaining the temperature at 130 ± 5 ° C. Then, it hold | maintained at reaction temperature (130 +/- 5 degreeC) for 1 hour, and collect | recovered after that. Neutralization was performed using KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.), followed by filtration to obtain a bleeding inhibitor (RE-1).

Comparative Example 2
A product using “New Pole BPE-100 (manufactured by Sanyo Chemical Co., Ltd.)” as it was was used as a bleeding inhibitor (RE-2).

Comparative Example 3
-Production of bleeding inhibitor (RE-3) In a pressure vessel equipped with a stirrer, a pressure gauge, and a thermometer, "New Pole BPE-40 (manufactured by Sanyo Chemical Co., Ltd., 2,2-bis (4-hydroxyphenyl) propane" 451.1 g of ethylene oxide total 4 mol adduct) ”and 1.5 g of potassium hydroxide were charged to all hydroxyl groups. Subsequently, after raising the temperature of the reaction system to 120 ° C., the system was dehydrated for 1 hour under reduced pressure. Thereafter, 1048.9 g of ethylene oxide was added to the reaction system over 5 hours at a gauge pressure of 0.4 MPa while maintaining the temperature at 150 ± 5 ° C. Then, it hold | maintained at reaction temperature (150 +/- 5 degreeC) for 1 hour, and collect | recovered after that. Neutralization was performed using Kyoward 600 (manufactured by Kyowa Chemical Industry Co., Ltd.), and filtration was performed to obtain a bleeding inhibitor (RE-3).

Comparative Example 4
-Production of bleeding inhibitor (RE-4) The bleeding inhibitor (RE-4) was prepared by changing the amount of potassium hydroxide to 3.0 g and further changing the amount of ethylene oxide as shown in Table 1. Manufactured in the same manner as Comparative Example 3.

  The contents of each bleeding inhibitor prepared above are summarized in Table 1.

The description in Table 1 will be described below.
* 1 “R ¹ ” in Formula (1) is a residue obtained by removing a hydroxyl group from the compound described in this column.
* 2 For RE-2, “New Pole BPE-100 (manufactured by Sanyo Chemical Co., Ltd.)” was used as it was.
m + n (average total added mole number) is the sum of “EO mole number” and “PO mole number”. For example, in Example 1, m + n (average total added mole number) is 80 + 0 = 80. .

(Evaluation of Examples 10 to 19 and Comparative Examples 5 to 9)
The following evaluation was performed by adding the bleeding inhibitor shown in Table 1 (bleeding inhibitor for hydraulic composition) to concrete.

Specifically, under the compounding conditions shown in Table 2, ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ube Mitsubishi Cement Co., Ltd., and Sumitomo Osaka Cement Co., Ltd.) was added to a 50 L forced biaxial mixer in a 20 ° C. test room. Hydraulic binder made of mixed, density = 3.16 g / cm ³ ) and land sand (Oikawa water system, density = 2.58 g / cm ³ ) and aggregate as aggregate (crushed stone from Okazaki, density = 2.66 g) / cm ³⁾ and added, further, "Chu Paul EX60 (manufactured by Takemoto Yushi Co.)" as an AE water reducing agent, each bleeding reduction agents shown in Table 1, and an air entraining agent AE-300 (manufactured by Takemoto Yushi Co.) And a predetermined amount (see Table 3) and "AFK-2 (manufactured by Takemoto Yushi Co., Ltd.)" which is an antifoaming agent, 0.005% with respect to the cement, and kneaded water (tap water) and the above 9 in the mixer Seconds was kneading. The concrete composition (hydraulic composition) was prepared by adjusting the amounts of the AE water reducing agent and the air entraining agent so that the slump was 18 ± 1 cm and the entrained air amount was 4.5 ± 0.5%.

  About the prepared concrete composition, the slump, the amount of entrained air, and the amount of bleeding were calculated, and the results are summarized in Table 3.

・ Entrained air volume (volume%):
The concrete composition immediately after mixing was measured according to JIS-A1128.

・ Slump (cm):
Simultaneously with the measurement of the amount of entrained air, it was measured according to JIS-A1101.

・ Bleeding amount:
The concrete composition immediately after kneading was measured according to JIS-A1123 after measuring the amount of entrained air and slump.

In Table 2, “cement” indicates the above-mentioned ordinary Portland cement. “Fine aggregate” indicates the above-mentioned land sand (Oikawa water system, density = 2.58 g / cm ³ ), and “Coarse aggregate” indicates crushed stone (Okazaki crushed stone, density = 2.66 g / cm ³ ). Indicates. The “fine aggregate ratio (%)” indicates a value calculated by the formula: fine aggregate / coarse aggregate × 100. “Water / cement ratio (%)” indicates a value calculated by the formula: water / cement × 100.

The description in Table 3 will be described below.
Amount added: Amount added relative to cement mass (%)
“% With respect to cement” means parts by mass with respect to 100 parts by mass of cement (hydraulic binder).

  As shown above, it has been found that the bleeding inhibitor of the present invention can reduce the amount of bleeding of the resulting hydraulic composition.

  The bleeding inhibitor of the present invention can be used as a bleeding inhibitor used in a hydraulic composition.

Claims (6)

A bleeding inhibitor for use in a hydraulic binder containing cement and a hydraulic binder containing water,
A bleeding inhibitor comprising a polyoxyalkylene compound represented by the following formula (1).

R: a residue obtained by removing all hydroxyl groups from a compound having 6 to 25 carbon atoms and two phenolic hydroxyl groups X and Y: each independently a hydrogen atom or 1 to 22 carbon atoms Alkyl group AO, BO: each independently an oxyalkylene group having 2 to 4 carbon atoms m, n: an integer of 1 to 299 and satisfying m + n = 60 to 300 The bleeding inhibitor according to claim 1, wherein, in the formula (1), R is a group having a bis (4-hydroxyphenyl) skeleton represented by the following formula (2).

However, in Formula (2), Z is a C1-C13 linear or branched alkylene group or a sulfonyl group.   In the formula (1), R is obtained by removing two hydroxyl groups from 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, or bis (4-hydroxyphenyl) sulfone. The bleeding inhibitor according to claim 1 or 2, which is a residue.   The bleeding inhibitor according to any one of claims 1 to 3, wherein in the formula (1), X and Y are hydrogen atoms.   The bleeding inhibitor according to any one of claims 1 to 4, wherein in the formula (1), 90 mol% or more of all oxyalkylene groups of AO and BO is an oxyethylene group.   In said Formula (1), m and n are the integers of 1-219, respectively, and m + n is an integer which satisfies 70-220, The bleeding inhibitor as described in any one of Claims 1-5. .