阅读说明：本技术 渗出抑制剂 (Bleeding inhibitor ) 是由 古田章宏 小林龙平 于 2018-11-30 设计创作，主要内容包括：提供可以得到能够抑制渗出的水硬性组合物的渗出抑制剂。该渗出抑制剂用于包含水和含有水泥的水硬性结合材料的水硬性组合物,且含有预定的聚氧化亚烷基化合物。(A bleeding inhibitor which can give a hydraulic composition capable of inhibiting bleeding. The bleeding inhibitor is used for a hydraulic composition comprising water and a hydraulic binder containing cement, and contains a predetermined polyoxyalkylene compound.)

1. A bleeding inhibitor for a hydraulic composition comprising water and a hydraulic binding material containing cement,

containing a polyoxyalkylene compound represented by the following formula (1),

[ chemical formula 1]

X-(OR²)_m-O-R¹-O-(R³O)_n-Y (1)

R¹: a residue obtained by removing all hydroxyl groups from a compound having an aromatic hydrocarbon group having 6 to 25 carbon atoms and 2 phenolic hydroxyl groups;

x, Y: each independently is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

OR²、R³O: each independently an oxyalkylene group having 2 to 4 carbon atoms;

m, n: is an integer of 1 to 299, and is an integer satisfying m + n of 60 to 300.

2. The exudation inhibitor according to claim 1, wherein, in the formula (1), R¹Is a group having a bis (4-hydroxyphenyl) skeleton represented by the following formula (2),

[ chemical formula 2]

Wherein Z in the formula (2) is a linear or branched alkyl group having 1 to 13 carbon atoms or a sulfonyl group.

3. The exudation inhibitor according to claim 1 or 2, wherein, in the formula (1), R¹Is a residue obtained by removing 2 hydroxyl groups from 2, 2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, or bis (4-hydroxyphenyl) sulfone.

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

5. The exudation inhibitor according to any one of claims 1 to 4, wherein, in the formula (1), OR²And R³90 mol% or more of all the oxyalkylene groups of O are oxyethylene groups.

6. The bleeding inhibitor according to any one of claims 1 to 5, wherein in the formula (1), m and n are each an integer of 1 to 219, and are integers satisfying that m + n is 70 to 220.

Technical Field

The present invention relates to a bleeding inhibitor. More specifically, the present invention relates to a bleeding inhibitor capable of obtaining a hydraulic composition in which bleeding is inhibited.

Background

Conventionally, hydraulic compositions have been widely used as cement compositions such as cement paste, mortar, and concrete. The hydraulic composition has the following problems: floating water (bleeding) occurs during the time from kneading with water until hardening.

When this bleeding occurs in large amounts after casting of the hydraulic composition, there are the following disadvantages: the passage of water generated when water in the hydraulic composition seeps out to the surface impairs the compactness of the structure of the hydraulic composition, thereby causing a decrease in strength at the time of hardening.

Therefore, in order to prevent this disadvantage, various additives for hydraulic compositions have been used, and among them, for example, polyethylene glycol has been used (see patent document 1).

Disclosure of Invention

Problems to be solved by the invention

However, the aggregate tends to be less permeable. Specifically, high-quality river sand, mountain sand, river gravel, mountain gravel, and the like have been used as the aggregate in the past, but recently, high-quality aggregates have been difficult to obtain, and crushed stone or crushed sand has been required as the aggregate. In this case, in order to obtain the same processing characteristics as those of the conventional aggregate, the unit water amount needs to be increased, but the increase in the unit water amount tends to increase the bleeding-out. Further, the polyethylene glycol described in patent document 1 may be difficult to sufficiently suppress and reduce bleeding. Therefore, there is a need for a bleeding inhibitor which does not easily affect other properties of a hydraulic composition and can sufficiently inhibit bleeding.

The present invention has been made in view of the problems of the prior art, and an object thereof is to provide a bleeding inhibitor which can obtain a hydraulic composition in which bleeding is inhibited.

Means for solving the problems

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

According to the present invention, the bleeding inhibitor shown below is provided.

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

[ chemical formula 1]

X-(OR²)_m-O-R¹-O-(R³O)_n-Y (1)，

R¹: a residue obtained by removing all hydroxyl groups from a compound having an aromatic hydrocarbon group having 6 to 25 carbon atoms and 2 phenolic hydroxyl groups;

x, Y: each independently is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

OR²、R³o: each independently an oxyalkylene group having 2 to 4 carbon atoms;

m, n: is an integer of 1 to 299, and is an integer satisfying m + n of 60 to 300.

[2]Above-mentioned [1]Wherein, in the above formula (1), R is¹Is a group having a bis (4-hydroxyphenyl) skeleton represented by the following formula (2),

[ chemical formula 2]

Wherein Z in the formula (2) is a linear or branched alkyl group having 1 to 13 carbon atoms or a sulfonyl group.

[3]Above-mentioned [1]Or [ 2]]Wherein, in the above formula (1), R is¹Is a residue obtained by removing 2 hydroxyl groups from 2, 2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, or bis (4-hydroxyphenyl) sulfone.

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

[5]Above-mentioned [1]To [4]]The bleeding inhibitor according to any one of the above formulae (1), wherein OR is²And R³90 mol% or more of all the oxyalkylene groups of O are oxyethylene groups.

[6] The bleeding-out inhibitor according to any one of the above [1] to [5], wherein in the above formula (1), m and n are each an integer of 1 to 219, and are an integer satisfying m + n of 70 to 220.

ADVANTAGEOUS EFFECTS OF INVENTION

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

Detailed Description

The embodiments of the present invention will be described below, but the present invention is not limited to the embodiments below, and it should be understood that technical solutions obtained by appropriately modifying, improving, etc. the embodiments below based on the general knowledge of those skilled in the art within the scope not departing from the gist of the present invention are also included in the scope of the present invention.

[1] Bleeding inhibitor:

the present invention is a bleeding inhibitor for a hydraulic composition comprising water and a hydraulic binder containing cement, containing a polyoxyalkylene compound represented by the following formula (1),

[ chemical formula 3]

X-(OR²)_m-O-R¹-O-(R³O)_n-Y (1)，

R¹: a residue obtained by removing all hydroxyl groups from a compound having an aromatic hydrocarbon group having 6 to 25 carbon atoms and 2 phenolic hydroxyl groups;

x, Y: each independently is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;

OR²、R³o: each independently an oxyalkylene group having 2 to 4 carbon atoms;

m, n: is an integer of 1 to 299, and is an integer satisfying m + n of 60 to 300.

[1-1] A polyoxyalkylene compound represented by the formula (1):

in the bleeding inhibitor of the present invention, R as in the polyoxyalkylene compound represented by the formula (1)¹Examples thereof include hydroquinone, catechol, binaphthol, 4' -biphenol, 2-bis(4-hydroxyphenyl) propane, 1-bis (4-hydroxyphenyl) -1-phenylethane, 2-bis (4-hydroxyphenyl) hexafluoropropane, 2-bis (4-hydroxyphenyl) butane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone, 5 '- (1-methylethylidene) -bis [1, 1' - (bisphenyl) -2-ol]And a residue obtained by removing a hydroxyl group from propane, 2-bis (4-hydroxyphenyl) hexafluoropropane, 1-bis (4-hydroxyphenyl) cyclohexane, and the like. As R¹A group (residue) having a bis (4-hydroxyphenyl) skeleton represented by the following formula (2) may be used. Of these, the residue obtained by removing 2 hydroxyl groups from 2, 2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, and bis (4-hydroxyphenyl) sulfone is preferable. These residues exhibit an excellent exudation-inhibiting effect.

[ chemical formula 4]

In the formula (2), Z represents a linear or branched alkyl group having 1 to 13 carbon atoms or a sulfonyl group.

Examples of X in formula (1) include a hydrogen atom and an alkyl group having 1 to 22 carbon atoms. Examples of the alkyl group having 1 to 22 carbon atoms include a methyl group, an ethyl group, a butyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a heneicosyl group, a docosyl group, a 2-methyl-pentyl group, a 2-ethyl-hexyl group, a 2-propyl-heptyl group, a 2-butyl-octyl group, a 2-pentyl-nonyl group, a 2-hexyl-decyl group, a 2-heptyl-undecyl group, a 2-octyl-dodecyl group, and a 2-nonyl-tridecyl group. Among them, X is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

Examples of Y in the formula (1) include the same groups as those of X.

Here, when X and Y are hydrogen atoms, they are preferable in terms of ease of synthesis of the compound, availability of raw materials, and economy.

OR in the formula (1)²Represents oxidation of 2 to 4 carbon atomsAn alkylene group. When there are multiple ORs²In this case, 2 or more kinds of oxyalkylene groups may be used. As OR ²Specifically, the ethylene oxide and/or propylene oxide is preferably contained, more preferably 50 mol% or more of the ethylene oxide, and still more preferably 90 mol% or more of the ethylene oxide. When 2 or more alkylene oxides are added, the order of bonding is not particularly limited, and the bonding may be random bonding or block bonding.

In addition, R in the formula (1)³O, with respect to OR²The same is said.

At OR²And R³In O, OR²And R³Preferably, 90 mol% or more of the total oxyalkylene groups in the total of O is oxyethylene. The bleeding-out suppressing effect is exhibited well.

In the formula (1), m and n represent the number of moles of polyoxyalkylene added, and m + n represents the total number of moles of polyoxyalkylene added. 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, preferably 70 ≦ m + n ≦ 220. If m + n is less than 60, the effect of reducing bleeding cannot be exhibited. If m + n is too large, the manufacturing cost is also increased, which is not practical.

The method for producing the polyoxyalkylene compound in which X and Y in the formula (1) are hydrogen atoms is not particularly limited, and the polyoxyalkylene compound can be produced by a known production method.

For example, the compounds can be prepared by reacting at R¹Wherein the compound having 2 phenolic hydroxyl groups is obtained by adding an alkylene oxide. Catalysts can be used in the addition of alkylene oxides. As the catalyst for addition polymerization of the alkylene oxide, an alkali catalyst such as an alkali metal, an alkaline earth metal, or a hydroxide or alcoholate thereof, a Lewis acid catalyst, or a composite metal catalyst can be used, and an alkali catalyst is preferable.

Examples of the alkali catalyst include sodium, potassium, sodium potassium amalgam, sodium hydroxide, potassium hydroxide, sodium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, potassium butoxide, and the like. Preferably sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide or potassium butoxide.

Examples of the lewis acid catalyst include, for example, tin tetrachloride, boron trifluoride diethyl ether complex, boron trifluoride di-n-butyl ether complex, boron trifluoride tetrahydrofuran complex, boron trifluoride phenol complex, boron trifluoride acetic acid complex and other boron trifluoride compounds.

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 only the polyoxyalkylene compound represented by the formula (1), but it is preferable to add an antioxidant.

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

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

The hydraulic binder contains cement. Examples of the cement include various portland cements such as ordinary portland cement, early strength portland cement, and normal heat cement, and various blended cements such as blast furnace cement, fly ash cement, and silica cement.

In order to obtain the effect as the bleeding-out reducing agent, the amount is preferably 0.01 to 3.0 parts by mass, more preferably 0.01 to 1.0 part by mass, and further preferably 0.02 to 0.5 part by mass, relative to 100 parts by mass of the hydraulic binder.