WO2022113725A1

WO2022113725A1 - Concrete release agent additive, concrete release agent, and concrete manufacturing method

Info

Publication number: WO2022113725A1
Application number: PCT/JP2021/041159
Authority: WO
Inventors: 郁香村松; 卓哉大石; 章宏古田
Original assignee: 竹本油脂株式会社
Priority date: 2020-11-27
Filing date: 2021-11-09
Publication date: 2022-06-02
Also published as: JP2022085817A; JP7064261B1; CN116507692A; JP6998094B1; JP2022085901A

Abstract

Provided is an additive (concrete release agent additive) for a concrete release agent with which a concrete cured product having excellent releasability and surface appearance can be obtained.　The concrete release agent additive is characterized by containing component (A) indicated by general formula (1).

Description

Auxiliary agent for concrete release agent, concrete release agent and concrete manufacturing method

The present invention relates to an auxiliary agent for a concrete release agent, a concrete release agent, and a method for manufacturing concrete. More specifically, the present invention relates to an auxiliary agent for a concrete release agent having improved peelability and surface aesthetics, a concrete release agent containing the auxiliary agent, and a method for producing concrete.

Conventionally, hardened concrete products such as concrete products have a problem that air bubble marks are generated on the surface due to air bubbles generated between the concrete product and the formwork at the time of its production. These bubble marks are not preferable from the viewpoint of durability and surface aesthetics of concrete products. Therefore, usually, after removing the mold from the formwork, the surface part is cut or the surface is embedded by applying mortar to process the surface condition of the hardened concrete. There is.

However, since such processing work is laborious and costly, a mold release agent that can suppress the generation of bubble marks on the surface of the hardened concrete has been reported (see, for example, Patent Documents 1 to 3). ..

Japanese Unexamined Patent Publication No. 2018-130957 Special Table No. 9-507181 Japanese Unexamined Patent Publication No. 6-278120

However, it is a new release agent that replaces the mold release agent and the like described in Patent Documents 1 to 3, and a new auxiliary agent that is blended therein, and has releasability from the formwork and bubbles of the obtained hardened concrete product. There has been a demand for the development of a release agent having few marks and a good surface appearance and an auxiliary agent to be blended with the release agent.

Therefore, in view of the above circumstances, the present invention satisfactorily exhibits the peelability of the hardened concrete from the formwork by blending it with the hardened concrete, and the surface of the hardened concrete after peeling. An object of the present invention is to provide an auxiliary agent (that is, an auxiliary agent for a concrete release agent) that improves the aesthetic appearance, a concrete release agent containing the auxiliary agent, and a method for producing concrete.

As a result of diligent research to solve the above-mentioned problem, the present inventors have found that the above-mentioned problem can be solved by containing a specific component (A). According to the present invention, the following auxiliary agents for concrete release agents, concrete release agents, and methods for producing concrete are provided.

[1] An auxiliary agent for a concrete release agent, which contains the component (A) represented by the following general formula (1).

(In the general formula (1), p is 0 or an integer of 1. R ¹ is a hydrocarbon group having 1 to 22 carbon atoms. R ² is an organic group represented by −X—H (provided that it is an organic group. X is a (poly) oxyalkylene group formed of 1 to 30 oxyalkylene groups having 2 to 4 carbon atoms, in which case p is 0), a methyl group, or a hydrogen atom. ³ is an organic group represented by −Y—H (where Y is a (poly) oxyalkylene group formed by 1 to 30 oxyalkylene groups having 2 to 4 carbon atoms (in this case, p is 0). (There is), and the organic group thereof is the organic group represented by -X-H or a hydrogen atom) and the organic group represented by -CH ² _- COMM ¹ (where M). ¹ is a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), or an organic amine, and the organic group represented by the _-CH2 -COM ¹ is a methyl group or a hydrogen atom in ^R2 . The total number of oxyalkylene groups represented by X and Y in R ² and R ³ is 3 to 40.)

[2] The auxiliary agent for a concrete release agent according to the above [1], which further contains the component (B) represented by the following general formula (2).

(In the general formula (2), R ⁴ is a hydrocarbon group having 6 to 22 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms. R ⁵ O is an oxyalkylene group having 2 to 4 carbon atoms. It is a group (however, when there are a plurality of the oxyalkylene groups, it can be one kind alone or two or more kinds). M ² is a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom). Alternatively, it is an organic amine. N is an integer of 0 to 20. M is an integer of 1 or 2.)

[3] The component (B) contains a component (P1) having m = 1 and a component (P2) having m = 2 in the general formula (2).
In the P-nuclear NMR measurement after the alkaline overneutralization pretreatment, when the total of the P-nuclear NMR integral ratios attributed to the component (P1) and the component (P2) is 100%,
The auxiliary agent for a concrete release agent according to the above [2], wherein the P-nuclear NMR integral ratio attributed to the component (P1) is 30 to 90%.

[4] When the total content ratio of the component (A) and the component (B) is 100 parts by mass.
The auxiliary agent for a concrete release agent according to any one of the above [2] and [3], which contains the component (A) in an amount of 1 to 99 parts by mass and the component (B) in a proportion of 1 to 99 parts by mass. ..

[5] The auxiliary agent for a concrete release agent according to the above [1], which further contains a component (C) which is at least one compound selected from a fatty acid having 8 to 30 carbon atoms and a salt thereof.

[6] When the total content ratio of the component (A) and the component (C) is 100 parts by mass.
The auxiliary agent for a concrete release agent according to the above [5], which contains the component (A) in an amount of 1 to 99 parts by mass and the component (C) in a proportion of 1 to 99 parts by mass.

[7] The auxiliary agent for a concrete release agent according to the above [2] or [3], which further contains a component (C) which is at least one compound selected from a fatty acid having 8 to 30 carbon atoms and a salt thereof.

[8] When the total content ratio of the component (A), the component (B), and the component (C) is 100 parts by mass.
The concrete according to the above [7], which contains the component (A) in an amount of 1 to 98 parts by mass, the component (B) in an amount of 1 to 98 parts by mass, and the component (C) in a proportion of 1 to 98 parts by mass. Auxiliary agent for release agent.

[9] A concrete release agent comprising the auxiliary agent for a concrete release agent according to any one of the above [1] to [8] and a base oil.

[10] When the total content of the concrete release agent auxiliary and the base oil is 100 parts by mass,
The concrete release agent according to the above [9], which contains 0.5 to 20 parts by mass of the auxiliary agent for a concrete release agent and 80 to 99.5 parts by mass of the base oil.

[11] The concrete release agent auxiliary agent according to any one of the above [1] to [8], the base oil, and the nonionic surfactant (excluding those corresponding to the component (A)). A concrete stripping agent characterized by containing.

[12] When the total content of the concrete release agent auxiliary, the base oil, and the nonionic surfactant is 100 parts by mass.
The concrete release agent auxiliary agent is contained in a proportion of 0.5 to 20 parts by mass.
The base oil is contained in a proportion of 60 to 98.5 parts by mass,
The concrete stripping agent according to the above [11], which contains the nonionic surfactant in a proportion of 1 to 20 parts by mass.

[13] A coating step of applying the concrete release agent according to the above [9] or [10] to the inner surface of a concrete formwork, and
The filling process of filling the formwork with the concrete forming material, which is the concrete material,
A method for producing concrete, comprising: a demolding step of demolding concrete, which is a material for forming concrete hardened in the formwork, from the formwork.

[14] A coating step of applying an aqueous solution of a concrete release agent, which is a mixture of the concrete release agent and water according to the above [11] or [12], to the inner surface of a concrete formwork.
The filling process of filling the formwork with the concrete forming material, which is the concrete material,
A method for producing concrete, comprising: a demolding step of demolding concrete, which is a material for forming concrete hardened in the formwork, from the formwork.

When the auxiliary agent for a concrete release agent of the present invention is blended with a concrete release agent, the concrete release agent exhibits good peelability of the hardened concrete product from the formwork, and bubbles in the hardened concrete product after peeling. It has the effect of improving the surface aesthetics with few marks.

The concrete release agent of the present invention has an effect of satisfactorily exhibiting the peelability of the hardened concrete from the formwork, having few bubble marks on the hardened concrete after peeling, and improving the surface appearance.

According to the method for producing concrete of the present invention, it is possible to satisfactorily peel off the hardened concrete from the formwork, and further, it is possible to produce the hardened concrete having few bubble marks and a good surface appearance. It is a thing.

Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. Therefore, it should be understood that the following embodiments can be appropriately modified, improved, or the like based on the ordinary 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 mass% and parts mean parts by mass.

(1) Auxiliary agent for concrete release agent:
The auxiliary agent for a concrete release agent of the present invention contains a specific component (A). By blending such an auxiliary agent for concrete release agent with the concrete release agent, the concrete release agent exhibits good peelability of the hardened concrete from the formwork, and the surface of the hardened concrete after peeling is exhibited. Improves aesthetics.

(1-1) Component (A):
The component (A) in the auxiliary agent for a concrete release agent of the present invention is a compound represented by the following general formula (1).

R ¹ in the general formula (1) is a hydrocarbon group having 1 to 22 carbon atoms, and among these, it is preferable that it has 6 to 22 carbon atoms. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent having excellent both peelability and surface aesthetics.

R ² in the general formula (1) is an organic group represented by —X—H (where X is a (poly) oxyalkylene group formed by 1 to 30 oxyalkylene groups having 2 to 4 carbon atoms. , In this case, p is 0), a methyl group, or a hydrogen atom. Regarding the oxyalkylene group having 2 to 4 carbon atoms, when a plurality of the oxyalkylene groups are present, one type alone or two or more types can be used.

R ³ in the general formula (1) is an organic group represented by —Y—H (where Y is a (poly) oxyalkylene group formed by 1 to 30 oxyalkylene groups having 2 to 4 carbon atoms (this). In the case, p is 0), and the organic group is represented by -CH ₂ -COMM ¹ (when R ² is the organic group or hydrogen atom represented by -X-H). An organic group (where M ¹ is a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), or an organic amine, and the organic group represented by the -CH ₂ -COM ¹ is R ² Is a methyl group or a hydrogen atom).

The total number of oxyalkylene groups represented by X and Y in R ² and R ³ in the general formula (1) is 3 to 40. That is, R ² and R ³ can adopt the above-mentioned predetermined (poly) oxyalkylene groups, but the total number of oxyalkylene groups at that time needs to be 3 to 40.

More specifically, the component (A) is a component (a1) which is a compound represented by the following general formula (1-1) and a component (a2) which is a compound represented by the following general formula (1-2). And so on.

(1-1a) Component (a1):
The component (a1) is a compound represented by the following general formula (1-1).

(However, in the general formula (1-1), R ¹ is a hydrocarbon group having 1 to 22 carbon atoms. R ⁶ O and R ⁷ O are independently oxyalkylene groups having 2 to 4 carbon atoms. (However, when a plurality of the oxyalkylene groups are present, one type can be used alone or two or more types can be used.) P is an integer of 0. Q and r are independently 0 to 30. An integer (however, an integer satisfying q + r = 3 to 40).

In R ¹ in the general formula (1-1), it is preferable to use a hydrocarbon group having 8 to 20 carbon atoms. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent having excellent both peelability and surface aesthetics.

R ⁶ O and R ⁷ O in the general formula (1-1) are independently oxyalkylene groups having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, one type alone or two or more types are present. Can be). That is, when a plurality of oxyalkylene groups are present, they may all be of the same type, for example, only an oxyalkylene group having 2 carbon atoms, or two or more kinds (for example, an oxyalkylene group having 2 carbon atoms and an oxy having 4 carbon atoms). It may be a combination of alkylene groups, etc.). It should be noted that, among the oxyalkylene groups having 2 to 4 carbon atoms, it is preferable that the oxyalkylene group having 2 carbon atoms is contained, and specifically, only the oxyalkylene group having 2 carbon atoms or the oxyalkylene group having 2 carbon atoms is used. It can be a combination of an oxyalkylene group having 2 carbon atoms and another oxyalkylene group (specifically, an oxyalkylene group having 3 carbon atoms). By doing so, it is possible to obtain an auxiliary agent for a concrete release agent having excellent both peelability and surface aesthetics.

In the general formula (1-1), q and r are independently integers of 0 to 30 (where q + r = 3 to 40), and in the general formula (1-1), q + r = 3 to 15. It is preferable that the compound satisfies the above conditions. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent having excellent both peelability and surface aesthetics.

Specific examples of the components represented by the general formula (1-1) include octylamine-polyoxyethylene adduct, decylamine-polyoxyethylene adduct, undecylamine-polyoxyethylene adduct, and dodecylamine-poly. Oxyethylene adduct, tridecylamine-polyoxyethylene adduct, tetradecylamine-polyoxyethylene adduct, pentadecylamine-polyoxyethylene adduct, hexadecylamine-polyoxyethylene adduct, 2-hexyldecylamine -Polyoxyethylene adduct, heptadecylamine-polyoxyethylene adduct, octadecylamine-polyoxyethylene adduct, nonadesylamine-polyoxyethylene adduct, icosylamine-polyoxyethylene adduct, henicosylamine-polyoxyethylene adduct Adducts, docosylamine-polyoxyethylene adducts, decenylamine-polyoxyethylene adducts, undecenylamine-polyoxyethylene adducts, dodecenylamine-polyoxyethylene adducts, tridecenylamine-polyoxyethylene adducts, tetradeceni Luamine-polyoxyethylene adduct, pentadecenylamine-polyoxyethylene adduct, hexadecenylamine-polyoxyethylene adduct, heptadecenylamine-polyoxyethylene adduct, octadecenylamine-polyoxyethylene adduct , Nonadesenylamine-polyoxyethylene adduct, icosenylamine-polyoxyethylene adduct, henicosenylamine-polyoxyethylene adduct, docosenylamine-polyoxyethylene adduct, beef adduct-polyoxyethylene adduct, cured Beef adduct-polyoxyethylene adduct; octylamine- (poly) oxyethylene / (poly) oxypropylene adduct, decylamine- (poly) oxyethylene / (poly) oxypropylene adduct, undecylamine- (poly) oxy Ethylene / (poly) oxypropylene adduct, dodecylamine- (poly) oxyethylene / (poly) oxypropylene adduct, tridecylamine- (poly) oxyethylene / (poly) oxypropylene adduct, tetradecylamine-( Poly) oxyethylene / (poly) oxypropylene adduct, pentadecylamine- (poly) oxyethylene / (poly) oxypropylene adduct, hexadecylamine- (poly) oxyethylene / (poly) oxypropylene adduct, 2 -Adduct Syldecylamine- (poly) oxyethylene / (poly) oxypropylene adduct, heptadecylamine- (poly) oxyethylene / (poly) oxypropylene adduct, octadecylamine- (poly) oxyethylene / (poly) oxypropylene Adduct, nonadesylamine- (poly) oxyethylene / (poly) oxypropylene adduct, icosylamine- (poly) oxyethylene / (poly) oxypropylene adduct, henicosylamine- (poly) oxyethylene / (poly) oxy Propropylene adduct, docosylamine- (poly) oxyethylene / (poly) oxypropylene adduct, decenylamine- (poly) oxyethylene / (poly) oxypropylene adduct, undecenylamine- (poly) oxyethylene / (poly) oxy Propropylene adduct, dodecenylamine- (poly) oxyethylene / (poly) oxypropylene adduct, tridecenylamine- (poly) oxyethylene / (poly) oxypropylene adduct, tetradecenylamine- (poly) oxyethylene / ( Poly) oxypropylene adduct, pentadecenylamine- (poly) oxyethylene / (poly) oxypropylene adduct, hexadecenylamine- (poly) oxyethylene / (poly) oxypropylene adduct, heptadecenylamine- (Poly) oxyethylene / (poly) oxypropylene adduct, octadecenylamine- (poly) oxyethylene / (poly) oxypropylene adduct, nonadesenylamine- (poly) oxyethylene / (poly) oxypropylene adduct , Icosenylamine- (poly) oxyethylene / (poly) oxypropylene adduct, henicosenylamine- (poly) oxyethylene / (poly) oxypropylene adduct, docosenylamine- (poly) oxyethylene / (poly) oxypropylene Examples thereof include adducts, beef adduct amine- (poly) oxyethylene / (poly) oxypropylene adduct, cured beef adduct amine- (poly) oxyethylene / (poly) oxypropylene adduct and the like.

(1-1b) Component (a2):
The component (a2) is a compound represented by the following general formula (1-2).

(However, in the general formula (1-2), R ¹ is a hydrocarbon group having 1 to 22 carbon atoms. R ⁸ is a hydrogen atom or a methyl group. P is an integer of 0 or 1. M ¹ is a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), or an organic amine.)

In R ¹ in the general formula (1-2), it is preferable to use a hydrocarbon group having 7 to 19 carbon atoms. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent having excellent both peelability and surface aesthetics.

R ⁸ in the general formula (1-2) is a hydrogen atom or a methyl group, and among these, a methyl group is preferable. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent having excellent both peelability and surface aesthetics.

P in the general formula (1-2) is an integer of 0 or 1, but p is preferably 1. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent having excellent both peelability and surface aesthetics.

M ¹ in the general formula (1-2) is a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom) or an organic amine, and among these, a hydrogen atom or an alkali metal is preferable. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent having excellent both peelability and surface aesthetics.

Examples of the component (a2) represented by the general formula (1-2) include N-lauroyl sarcosine, N-oleoyl sarcosine, N-cocoyl sarcosine, sarcosine, N-ethyl glycine, N-acetyl glycine and the like. Salt and the like can be mentioned.

(1-2) Component (B):
The auxiliary agent for a concrete release agent of the present invention preferably further contains the component (B) represented by the following general formula (2). By blending the auxiliary agent for concrete release agent further containing such a component (B) with the concrete release agent, the concrete release agent further exhibits the release property of the hardened concrete from the formwork and peels off. The surface aesthetics of the later hardened concrete will be further improved.

R ⁴ in the general formula (2) is a hydrocarbon group having 6 to 22 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms, and among these, a hydrocarbon having 8 to 18 carbon atoms. That's good. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent having excellent both peelability and surface aesthetics.

Examples of ^R4 in the general formula (2) include hexyl alcohol, heptyl alcohol, octyl alcohol, 2-ethyl-hexyl alcohol, nonyl alcohol, decyl alcohol, 2-propyl-heptyl alcohol, undecyl alcohol, and dodecyl alcohol. A hydroxyl group from an aliphatic alcohol having 6 to 22 carbon atoms such as 2-butyl-octyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, isostearyl alcohol, oleyl alcohol, eicosyl alcohol, and docosyl alcohol. Residues excluded; Residues obtained by removing hydroxyl groups from phenols having 6 to 30 carbon atoms such as phenols, cumylphenols, octylphenols, nonylphenols, phenylphenols, monostyrene phenols, and distyreneated phenols; hexyl alcohols, heptyl alcohols, Octyl alcohol, 2-ethyl-hexyl alcohol, nonyl alcohol, decyl alcohol, 2-propyl-heptyl alcohol, undecyl alcohol, dodecyl alcohol, 2-butyl-octyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl At least one of ethylene oxide and propylene oxide is added in a total ratio of 1 to 20 mol per mol of an aliphatic alcohol having 6 to 22 carbon atoms such as alcohol, isostearyl alcohol, oleyl alcohol, eicosyl alcohol, and docosyl alcohol. Residues obtained by removing hydroxyl groups from Residues obtained by adding hydroxyl groups in a total ratio of 1 to 20 mol; and the like.

R ⁵ O in the general formula (2) is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, one type alone or two or more types can be used). Among these, it is often an oxyalkylene group having 2 carbon atoms, and further, it is preferable that 50 mol% or more of the oxyalkylene group having 2 carbon atoms is contained in the oxyalkylene group having 2 to 4 carbon atoms. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent having excellent both peelability and surface aesthetics.

M ² in the general formula (2) is a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), or an organic amine. Among these, a hydrogen atom or an organic amine is preferable. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent having excellent both peelability and surface aesthetics.

N in the general formula (2) is an integer of 0 to 20, preferably an integer of 0 to 10. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent having excellent both peelability and surface aesthetics.

M in the general formula (2) is an integer of 1 or 2. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent having excellent both peelability and surface aesthetics.

(P-nuclear NMR integral ratio)
The component (B) can contain a component (P1) having m = 1 in the general formula (2) and a component (P2) having m = 2. In this case, in the P-nuclear NMR measurement after the alkali overneutralization pretreatment, when the total of the P-nuclear NMR integral ratios attributed to the component (P1) and the component (P2) is 100%, the component (P1) ), The P-nuclear NMR integral ratio is preferably 30 to 90%, more preferably 35 to 80%, and even more preferably 40 to 75%. With such a configuration, it is possible to obtain an auxiliary agent for a concrete release agent, which is further excellent in both peelability and surface aesthetics.

Here, the "alkali overneutralization pretreatment" in the present specification is a pretreatment in which an excessive amount of alkali is added to the acid remaining in the component (B), and a conventionally known method is adopted. Can be done. Specific examples of the alkali are not particularly limited, and examples thereof include hydroxides of alkali metals or alkaline earth metals. Further, it may be the same as or different from the alkali used when synthesizing the component (a1). Specific examples of hydroxides of alkali metals or alkaline earth metals include sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and the like.

³¹ In the measurement of P-NMR, by performing this "alkali overneutralization pretreatment" with an appropriate amount of alkali, the peaks attributed to the component (P1) and the component (P2) can be clearly separated. It is possible to calculate the P nuclear integral ratio attributed to the compound.

The P-nuclear NMR integral ratio attributed to the component (P1) can be calculated as follows, for example. That is, the measurement when the component (B) was subjected to alkaline overneutralization treatment and subjected to ³¹ P-NMR (trade name MERCURY plus NMR Spectrometer System, 300 MHz manufactured by VALIAN) under the condition that the pH was 12 or higher. Using the values, it is calculated based on the following equations (a) and (b). As the solvent, a mixed solvent of heavy water / tetrahydrofuran = 8/2 (volume ratio) can be used.

In addition, in the formula (a) and the formula (b), "P conversion 1" is an alkali metal salt or the like of the component (P1) in which m = 1 among the components (B) represented by the general formula (2). The attributed P-nuclear NMR integrated value is shown, and "P-formation 2" is attributed to the alkali metal salt or the like of the component (P2) having m = 2 among the components (B) represented by the general formula (2). The P-nuclear NMR integrated value is shown.

When the auxiliary agent for a concrete release agent of the present invention contains the component (A) and the component (B) (when the component (C) is not contained), the blending ratio of these is not particularly limited, but is as follows. It is preferable to do so. That is, when the total content ratio of the component (A) and the component (B) is 100 parts by mass, the component (A) is contained in a ratio of 1 to 99 parts by mass, and the component (B) is contained in 1 to 99 parts by mass. It is preferable to contain in the ratio of. With such a blending ratio, an auxiliary agent for a concrete release agent, which is further excellent in both peelability and surface aesthetics, can be obtained. A more preferable blending ratio of the component (A) is 5 to 95 parts by mass, and a particularly preferable ratio is 5 to 90 parts by mass. The more preferable blending ratio of the component (B) is 5 to 95 parts by mass, and the particularly preferable ratio is 10 to 95 parts by mass.

(1-3) Component (C):
The auxiliary agent for a concrete release agent of the present invention preferably further contains a component (C) which is at least one compound selected from a fatty acid having 8 to 30 carbon atoms and a salt thereof. By further containing the component (C), an auxiliary agent for a concrete release agent, which is further excellent in both peelability and surface aesthetics, can be obtained. More specifically, the component (C) improves the peelability between the formwork and the hardened concrete (hydraulic composition), and suppresses the generation of bubble marks formed on the surface of the hardened concrete.

The component (C) is at least one selected from the group consisting of a fatty acid having 8 to 30 carbon atoms and a salt thereof, and among these, a fatty acid having 8 to 24 carbon atoms and a salt thereof are preferable. Fatty acids having 8 to 22 carbon atoms and salts thereof are preferable. If the number of carbon atoms is less than 8, the effect of improving the peelability and the surface aesthetics may not be sufficient.

Examples of the component (C) include capric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, lysynolic acid, arachidic acid, behenic acid, lignoseric acid, and serotic acid. , Palmitic acid, melicic acid, isostearic acid, erucic acid, 12-hydroxystearic acid and the like, and salts thereof. Further, examples thereof include tall oil fatty acid, coconut oil fatty acid, beef fat fatty acid, castor oil fatty acid, lanolin fatty acid and the like, which are mixtures thereof, and salts thereof.

When the auxiliary agent for a concrete release agent of the present invention contains the component (A) and the component (C) (when the component (B) is not contained), the blending ratio of these is not particularly limited, but is as follows. It is preferable to do so. That is, when the total content ratio of the component (A) and the component (C) is 100 parts by mass, the component (A) is contained in a ratio of 1 to 99 parts by mass, and the component (C) is contained in 1 to 99 parts by mass. It is preferable to contain in the ratio of. With such a blending ratio, an auxiliary agent for a concrete release agent, which is further excellent in both peelability and surface aesthetics, can be obtained. A more preferable blending ratio of the component (A) is 4 to 93 parts by mass, and a particularly preferable ratio is 6 to 90 parts by mass. The more preferable blending ratio of the component (C) is 7 to 96 parts by mass, and the particularly preferable ratio is 10 to 94 parts by mass.

When the auxiliary agent for a concrete release agent of the present invention contains the component (A), the component (B), and the component (C), the blending ratio thereof is not particularly limited, but it is preferably as follows. .. That is, when the total content of the component (A), the component (B), and the component (C) is 100 parts by mass, the component (A) is contained in a ratio of 1 to 98 parts by mass, and the component (B) is contained. Is preferably contained in a proportion of 1 to 98 parts by mass, and the component (C) is preferably contained in a proportion of 1 to 98 parts by mass. With such a blending ratio, an auxiliary agent for a concrete release agent, which is further excellent in both peelability and surface aesthetics, can be obtained. A more preferable blending ratio of the component (A) is 3 to 92 parts by mass, and a particularly preferable ratio is 10 to 89 parts by mass. The more preferable blending ratio of the component (B) is 3 to 90 parts by mass, and the particularly preferable ratio is 8 to 87 parts by mass. The more preferable blending ratio of the component (C) is 2 to 94 parts by mass, and the particularly preferable ratio is 3 to 82 parts by mass.

(1-4) Other ingredients:
The auxiliary agent for a concrete release agent of the present invention may further contain other components in addition to the above-mentioned components (A) to (C).

Examples of other components include the component (D) represented by the following general formula (3). When the component (D) is contained, an auxiliary agent for a concrete release agent having excellent both peelability and surface aesthetics can be obtained.

(However, in the general formula (3), R ⁹ is a hydrocarbon group having 8 to 22 carbon atoms. R ¹⁰ and R ¹¹ are independently methyl groups, ethyl groups or hydroxyethyl groups, respectively.)

R ⁹ in the general formula (3) is a hydrocarbon group having 8 to 22 carbon atoms, and among these, it is preferable that it has 8 to 18 carbon atoms. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent having excellent both peelability and surface aesthetics.

R ¹⁰ and R ¹¹ in the general formula (3) are each independently a methyl group, an ethyl group or a hydroxyethyl group, and among these, a methyl group is preferable. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent having excellent both peelability and surface aesthetics.

Examples of the component (D) represented by the general formula (3) include octyldimethylamine oxide, nonyldecyldimethylamine oxide, decyldimethylamine oxide, undecyldimethylamine oxide, dodecyldimethylamine oxide, and tridecyldimethylamine oxide. Mystylyldimethylamine Oxide, Pentadecyldimethylamine Oxide, Hexadecyldimethylamine Oxide, Heptadecyldimethylamine Oxide, Stearyldimethylamine Oxide, Nonadecyldimethylamine Oxide, Icosyldimethylamine Oxide, Eikosyldimethylamine Oxide, Heneikosyl Examples thereof include dimethylamine oxide, docosyldimethylamine oxide, oleyldimethylamine oxide, coconut oil dimethylamine oxide, coconut oil diethylamine oxide, lauryldihydroxyethylamine oxide and the like.

Examples of other components include raw materials for components A, B, and C, by-products and impurities derived from synthetic methods, and the like.

The content ratio of other components may be, for example, 0 to 10% by mass of the total amount of the auxiliary agent for concrete release agent of the present invention.

(2) Concrete release agent:
The concrete stripping agent contains a base oil as a main agent and further contains an auxiliary agent for a concrete stripping agent as an additive. Such concrete release agents include water-based type release agents and oil-based type release agents, and these water-based type release agents and oil-based type release agents are appropriately selected depending on the concrete material and purpose of use. It is used.

The above-mentioned auxiliary agent for concrete stripping agent of the present invention can be blended in both water-based type and oil-based type, and can satisfactorily improve peelability and surface aesthetics. That is, the above-mentioned auxiliary agent for concrete release agent of the present invention is good for both water-based (water-based) release agents and oil-based (oil-based) release agents. Can be adopted for.

Hereinafter, the oil-based concrete release agent and the water-based concrete release agent in the present invention will be described.

(2-1) Oil-based concrete release agent:
The oil-based concrete release agent contains a base oil as a main agent and the above-mentioned auxiliary agent for the concrete release agent of the present invention, and is used as it is without adding water at the time of use.

The base oil is not particularly limited, and a base oil used as a conventionally known concrete release agent can be appropriately selected and used. For example, mineral oils such as kerosene, light oil, spin oil, trans oil, machine oil; synthetic oils such as polyalphaolefins and polyol esters; vegetable oils such as rapeseed, palm, palm, soybean and sesame oil; fats and oils; fatty acid esters and the like. Can be mentioned. Among these, at least one selected from the group consisting of mineral oils, synthetic oils and vegetable oils is preferable.

This oil-based concrete release agent contains 0.5 to 20 parts by mass of the concrete release agent auxiliary agent when the total content of the concrete release agent auxiliary agent and the base oil is 100 parts by mass. , The base oil is preferably contained in a proportion of 80 to 99.5 parts by mass. By doing so, the peelability of the hardened concrete product from the formwork can be further exhibited, the number of air bubble marks in the hardened concrete product after peeling can be reduced, and the surface appearance can be further improved.

The more preferable blending ratio of the auxiliary agent for concrete release agent is 1 to 19 parts by mass, and the particularly preferable ratio is 1 to 18 parts by mass. The more preferable mixing ratio of the base oil is 81 to 99 parts by mass, and the particularly preferable ratio is 82 to 99 parts by mass.

The oil-based concrete release agent can further contain other additives in addition to the base oil and the auxiliary agent for the concrete release agent.

Examples of other additives include by-products contained in the base oil.

The content ratio of other additives can be, for example, 0 to 10% by mass of the entire oil-based concrete release agent.

(2-2) Water-based concrete release agent:
The water-based concrete release agent contains a base oil as a main agent, the above-mentioned auxiliary agent for the concrete release agent of the present invention, and a nonionic surfactant (excluding those corresponding to the above-mentioned component (A)). It is used by adding water on the spot when using it, or by diluting it with water in advance.

The base oil is not particularly limited, and the same base oil as the base oil blended in the oil-based concrete release agent described above can be appropriately selected and used.

The nonionic surfactant is not particularly limited, and a nonionic surfactant used in a conventionally known concrete stripping agent can be appropriately selected and adopted. Examples of the nonionic surfactant include alkyl alcohol, alkylene alcohol and its alkylene oxide adduct, alkylphenol and its alkylene oxide adduct, mono (or di, tri) styrylphenol-alkylene oxide adduct, and castor oil-alkylene oxide adduct. Examples thereof include hardened castor oil-alkylene oxide adduct, sorbitan fatty acid ester and its alkylene oxide adduct, (poly) glycerin fatty acid ester and its alkylene oxide adduct, sucrose fatty acid ester and its alkylene oxide adduct. .. Since the component (A) may correspond to a nonionic surfactant, in the present invention, a nonionic surfactant is used.

This water-based concrete release agent contains 0.5 to 20 parts by mass of the concrete release agent auxiliary agent when the total content of the concrete release agent auxiliary agent, the base oil, and the nonionic surfactant is 100 parts by mass. It is preferable to contain the base oil in a proportion of 60 to 98.5 parts by mass and the nonionic surfactant in a proportion of 1 to 20 parts by mass. By doing so, the peelability of the hardened concrete product from the formwork can be further exhibited, the bubble marks in the hardened concrete product after peeling can be made smaller, and the surface appearance can be further improved.

The more preferable blending ratio of the auxiliary agent for concrete release agent is 1 to 18 parts by mass, and the particularly preferable ratio is 1 to 16 parts by mass. The more preferable mixing ratio of the base oil is 65 to 95 parts by mass, and the particularly preferable ratio is 75 to 89 parts by mass. The more preferable blending ratio of the nonionic surfactant is 1 to 18 parts by mass, and the particularly preferable ratio is 1 to 15 parts by mass.

The water-based concrete release agent can further contain other additives in addition to the base oil, the concrete release agent auxiliary agent, the nonionic surfactant, and water.

Examples of other additives include by-products contained in the base oil and by-products such as polyalkylene oxides produced when synthesizing nonionic surfactants.

The content ratio of other additives can be, for example, 1 to 10% by mass of the entire water-based concrete release agent.

(3) Use of concrete release agent:
The concrete release agent of the present invention can be used as a release agent for removing the hardened concrete from the formwork in the production of concrete (hardened concrete). The type, material, and composition of the hardened concrete are not particularly limited. That is, the concrete stripping agent of the present invention can be satisfactorily used as a stripping agent for stripping a hardened concrete made of a conventionally known material. The formwork is usually made of metal such as steel or wooden, but the concrete release agent of the present invention is used by applying it to a conventionally known formwork without limitation on the material of the formwork. can do.

(4) Concrete manufacturing method:
The method for producing concrete of the present invention is a coating step of applying the above-mentioned concrete release agent of the present invention or an aqueous liquid obtained by diluting the concrete with water to the inner surface of a concrete formwork, and a concrete material. It is a method including a filling step of filling a concrete forming material into a formwork and a demolding step of removing concrete, which is a concrete forming material hardened in the formwork, from the formwork. According to such a manufacturing method, since the concrete release agent of the present invention described above is adopted, the hardened concrete can be satisfactorily peeled from the formwork, and further, there are few bubble marks and the surface appearance is good. Hardened concrete can be produced. The concrete forming material is concrete (ready-mixed concrete) that has not yet hardened.

(4-1) Coating process:
The formwork for concrete is not particularly limited, and conventionally known formwork for concrete can be appropriately adopted. The formwork may be made of metal such as steel, wood, synthetic resin, or the like.

The method of applying the concrete release agent or the aqueous liquid to the inner surface of the formwork is not particularly limited, and for example, application by a brush or spraying by a spray or the like can be adopted.

It is preferable that the concrete release agent is evenly applied to the entire inner surface of the formwork. The thickness of the coating layer of the concrete release agent is not particularly limited and can be appropriately set.

When a water-based concrete release agent is used, the concrete release agent can be dried after applying it to the inner surface of the formwork and before filling the ready-mixed concrete. The drying conditions are not particularly limited and can be set as appropriate.

(4-2) Aqueous liquid preparation process:
When a water-based concrete release agent is adopted, the method for producing concrete of the present invention can further include a water-based liquid preparation step. In the aqueous liquid preparation step, before the above-mentioned coating step, a concrete stripping agent containing a nonionic surfactant (excluding those corresponding to the component (A)) is used, and the concrete stripping agent and the concrete stripping agent are used. This is a step of mixing with water to prepare an aqueous solution of a concrete release agent.

As the nonionic surfactant, the above-mentioned nonionic surfactant can be appropriately adopted.

The ratio of the concrete release agent to the aqueous solution of the concrete release agent is not particularly limited and can be appropriately set, but can be, for example, about 1 to 99% by mass. It is preferably 10 to 99% by mass. If the proportion of the concrete release agent is too small, the release property may decrease.

When an oil-based concrete release agent is used, this oil-based concrete release agent can be applied to the inner surface of the formwork as it is.

(4-3) Filling process:
The method of filling the ready-mixed concrete into the formwork is not particularly limited, and a method of pouring the ready-mixed concrete into the formwork with a single operation can be adopted. Further, after filling, compaction may be performed using a rod-shaped vibrator, a formwork vibrator, or the like.

The concrete forming material (hydraulic composition), which is a concrete material, is not particularly limited, and a conventionally known concrete material (hydraulic composition) can be appropriately adopted.

(4-4) Curing process:
Usually, a curing process of filling the formwork with ready-mixed concrete and then hardening the concrete can be adopted. In the method for producing concrete of the present invention, there is no particular limitation on the curing method until the concrete is hardened, and a conventionally known method can be appropriately adopted. For example, the concrete-filled formwork may be cured while being exposed to the outside air temperature, or the curing time may be shortened by heating at about 30 to 120 ° C. for a desired time using steam or an autoclave. good.

(4-5) Demolding process:
The method for producing concrete of the present invention further includes a demolding step of removing the concrete, which is a material for forming concrete hardened in the formwork, from the formwork.

The method of removing the hardened concrete from the formwork is not particularly limited, and a conventionally known method can be appropriately adopted. In the present invention, by using the above-mentioned concrete release agent of the present invention or an aqueous liquid obtained by diluting the concrete with water, the demolding of the hardened concrete in the present demolding step becomes easy (that is, the releasability). Will be good).

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

In the following synthesis examples 1 to 6, a method for synthesizing the components (A-1) to (A-3), (A-7), and (A-8) corresponding to the component (A) will be described.

(Synthesis Example 1) Synthesis of component (A-1):
533.3 g of dodecylamine was charged in the autoclave. Then, the inside of the autoclave was sufficiently replaced with nitrogen, and the temperature was maintained at 155 ° C. with stirring, and 237.6 g of ethylene oxide was press-fitted so as to maintain a pressure of 0.6 MPa. Then, it was aged at the temperature for 0.5 hour. Next, the temperature was maintained at 100 ° C., and 237.6 g of ethylene oxide was press-fitted so as to maintain a pressure of 0.6 MPa. Then, it was aged at the temperature for 1 hour to complete the reaction, and the component (A-1) corresponding to the component (A) was obtained.

(Synthesis Example 2) Synthesis of component (A-2):
The component (A-2) corresponding to the component (A) was synthesized in the same manner as the component (A-1) except that the raw materials and the charging ratio were changed.

(Synthesis Example 3) Synthesis of component (A-3):
The autoclave was charged with 1478.5 g of octadecylamine. Then, the inside of the autoclave was sufficiently replaced with nitrogen, and the temperature was maintained at 150 ° C. with stirring, and 483.3 g of ethylene oxide was press-fitted so as to maintain a pressure of 0.5 MPa. Then, it was aged at the temperature for 0.5 hour and cooled to 60 ° C. Then, 10.0 g of potassium hydroxide powder was added as a catalyst. Then, the inside of the autoclave was sufficiently replaced with nitrogen and dehydrated, and the temperature was maintained at 120 ° C. with stirring, and 483.3 g of ethylene oxide was press-fitted while maintaining a pressure of 0.5 MPa. Then, the mixture was aged at the temperature for 1 hour, then the temperature was raised to 150 ° C., and 2548.9 g of 1,2-propylene oxide was press-fitted while maintaining a pressure of 0.5 MPa. Then, it was aged at the said temperature for 1 hour to complete the reaction, and the component (A-3) corresponding to the component (A) was obtained.

(Synthesis Examples 4 and 5) Synthesis of components (A-7) and (A-8):
The components (A-7) and (A-8) corresponding to the component (A) were synthesized in the same manner as the component (A-3) except that the raw materials and the charging ratio were changed.

Next, in the following synthesis examples 6 to 11, a method for synthesizing the components (B-1) to (B-6) corresponding to the component (B) will be described.

(Synthesis Example 6) Synthesis of component (B-1):
915.3 g of an adduct of 4 mol of oleyl alcohol-ethylene oxide was charged in a reaction vessel, and 96.6 g of diphosphorus pentoxide was added at 55 ° C. with stirring. After aging at 80 ° C. for 3 hours, the mixture was cooled to 50 ° C. or lower to obtain a component (B-1) corresponding to the component (B).

(Synthesis Examples 7-9) Synthesis of components (B-2) to (B-4):
The components (B-2) to (B-4) corresponding to the component (B) were synthesized in the same manner as the component (B-1) except that the raw materials and the charging ratio were changed.

(Synthesis Example 10) Synthesis of component (B-5):
450.0 g of a 12 mol adduct of distyrene phenol-ethylene oxide was charged in a reaction vessel, and 24.1 g of diphosphorus pentoxide was added at 50 ° C. with stirring. After aging at 70 ° C. for 3 hours, it was neutralized by adding 2.0 g of a 48% potassium hydroxide aqueous solution and 0.1 g of calcium hydroxide at 50 ° C. Then, the water was distilled off under reduced pressure at 90 ° C. to obtain a component (B-5) corresponding to the component (B).

(Synthesis Example 11) Synthesis of component (B-6):
The component (B-6) corresponding to the component (B) was synthesized in the same manner as the component (B-5) except that the raw materials and the charging ratio were changed.

Next, the components (A) shown in Table 1 below were used, and the components (B) used were those shown in Table 2 below.

In Table 1, commercially available products were used as "A-4" to "A-6" and "A-10". As "A-9", 100 g of commercially available sarcosine was diluted, stirred and neutralized in water with 0.41 g of calcium hydroxide, and then water was distilled off under reduced pressure.

In Table 2, the column of "P nuclear integral ratio (%)" is when the total of the P nuclear NMR integral ratios attributed to the component (P1) and the component (P2) among the components (B) is 100%. , "P-nuclear NMR integral ratio attributed to component (P1)" and "P-nuclear NMR integral ratio attributed to component (P2)" are shown. The components (B-1) to (B-6) are a mixture of the one having m of 1 and the one having m of 2 in the general formula (2).

The P-nuclear NMR integration ratio of the component (P1) and the component (P2) in the component (B) represented by the general formula (2) is determined by adding excess KOH to an alkali metal salt of an aliphatic alcohol phosphate or the like to adjust the pH. Using the measured values when subjected to ³¹ P-NMR (trade name MERCURY plus NMR Spectrometer System, 300 MHz) under the condition of 12 or more, the following equations (a) and (b) were used. Calculated based on. As the solvent, a mixed solvent of heavy water / tetrahydrofuran = 8/2 (volume ratio) was used.

Here, in the formulas (a) and (b), "P conversion 1" is an alkali metal salt or the like of the component (P1) in which m = 1 among the components (B) represented by the general formula (1). The P-nuclear NMR integrated value attributed to is shown, and "P-formation 2" belongs to the alkali metal salt of the component (P2) having m = 2 among the components (B) represented by the general formula (1). The P-nuclear NMR integrated value to be obtained is shown.

Next, the components (C) shown in Table 3 below were used, and the components (D) used were those shown in Table 4 below.

In Table 3, "C-1" is oleic acid (manufactured by VANTAGE, VOLEIC OA10), and "C-2" is tall oil fatty acid (manufactured by Harima Chemicals, Hartall FA-1P). In addition, in Tables 3 and 4, as in the case of the above-mentioned "C-1" and "C-2", commercially available products were used for those not particularly described.

Next, as shown in Table 5, an auxiliary agent for a concrete release agent was prepared using each component. For those containing water, the water was distilled off under reduced pressure to formulate the mixture.

In Table 5, "R-2" is a lauryl alcohol EO 10 mol adduct (manufactured by Takemoto Oil & Fat Co., Ltd.), and "R-3" is an oleyl alcohol EO6PO 40 mol adduct (manufactured by Takemoto Oil & Fat Co., Ltd.).

(Examples 1 to 52, Comparative Examples 1 to 14)
Next, as shown in Tables 6 and 7, each component was mixed to prepare a concrete release agent. Examples 1 to 39 and Comparative Examples 1 to 9 in Table 6 show oil-based concrete release agents, and Examples 40 to 52 and Comparative Examples 10 to 14 in Table 7 show water-based concrete release agents. Shows. Further, in Table 7, the mass part of "water" indicates the mass part with respect to a total of 100 parts by mass of the base oil, the auxiliary agent for concrete release agent, and the nonionic surfactant.

The "base oil" in Tables 6 and 7 is shown in Table 9 below. Further, in Table 7, "nonionic surfactant" is shown in Table 10 below. In Table 9, Pure Safety 32 and Pure Spin D are both manufactured by Cosmo Oil Co., Ltd., and Diana Fresia U-46 is manufactured by JXTG Energy Co., Ltd. Moreover, these are all spin oils.

(Evaluation test)
The evaluation methods for each of the following evaluations (formulation stability, emulsion stability, peelability, surface aesthetics) of the prepared concrete release agent are shown below.

In order to evaluate "peeling property" and "surface aesthetics", a hydraulic composition (concrete material) was prepared as follows.

(Preparation of hydraulic composition (concrete material))
In a constant temperature room with a temperature of 20 ° C. and a humidity of 80%, all the ingredients and admixtures shown in Table 11 were put together in a 50 L bread-type forced kneading mixer under the formulation conditions shown in Table 11 and kneaded for 90 seconds. Prepared concrete. The prepared concrete was filled in a steel formwork within 15 minutes after kneading. The concrete had a concrete temperature of 21 ° C., an air volume of 5.0%, and a slump of 18.0 cm.

As an admixture, a high-performance water reducing agent (Tupole NV-80 (JIS A 6204), 0.7% by mass with respect to cement), an AE agent (AE-300 (JIS A 6204), with respect to cement). 0.0025% by weight) was used as part of the kneaded water.

The specific contents of the materials used are as follows.
Cement: Ordinary Portland cement (equal mixture of Taiheiyo Cement Co., Ltd., Ube-Mitsubishi Cement Co., Ltd. and Sumitomo Osaka Cement Co., Ltd.) Density 3.16 g / cm ³
Water: Gamagori City Waterworks Fine Aggregate: Oi River Water System Land Sand Density 2.58 g / cm ³
Coarse aggregate: Crushed stone from Okazaki Density 2.68 g / cm ³

(Pharmaceutical stability)
A test solution, which is a concrete stripping agent obtained by mixing a base oil and an auxiliary agent for a concrete stripping agent, was placed in a 250 mL transparent plastic container with a lid, and then allowed to stand at 20 ° C.

Then, the state of the test solution during standing was appropriately confirmed visually (specifically, 1 week, 2 weeks, and 4 weeks after the start of standing) and evaluated. The evaluation criteria are shown below. The evaluation results are shown in Tables 6 and 8.

S: When it is confirmed that the test solution is uniform when the confirmation is performed 4 weeks after the start of standing A: The test solution is uniform when the confirmation is performed 2 weeks after the start of standing. However, when the test solution was not uniform when the confirmation was performed at the 4th week, B: The test solution was uniform when the confirmation was performed at the 1st week after the start of standing. When the test solution is not uniform when the confirmation is performed at the week C: When the test solution is not uniform when the confirmation is performed at the first week after the start of standing.

(Emulsification stability)
50 g of the prepared concrete stripping agent test solution was placed in a 250 mL transparent plastic container with a lid, 200 g of Gamagori-shi tap water was added, and the mixture was shaken well and allowed to stand at 20 ° C.

Then, the state of the test solution during standing was appropriately confirmed visually (specifically, 1 hour, 6 hours, and 12 hours after the start of standing) and evaluated. The evaluation criteria are shown below. The evaluation results are shown in Table 8.

S: When it is confirmed that the test solution is uniformly emulsified and cloudy when the confirmation is performed 12 hours after the start of standing A: The confirmation is performed 6 hours after the start of standing. When it was confirmed that the test solution was uniformly emulsified and clouded, but it was not found that the test solution was uniformly emulsified and clouded when the confirmation was performed at the 12th hour. B: It was confirmed that the test solution was uniformly emulsified and clouded when the confirmation was performed 1 hour after the start of standing, but the test solution was confirmed when the confirmation was performed 6 hours. When it is not recognized that it is uniformly emulsified or cloudy C: When it is not recognized that the test solution is uniformly emulsified or cloudy when the confirmation is performed 1 hour after the start of standing.

(Removability)
The prepared concrete release agent was uniformly applied to the entire inner surface of a bottomed cylindrical steel formwork having an inner diameter of 10 cm and a height of 20 cm using a brush. After that, it was allowed to stand for 1 hour or more with the bottom surface turned upside down so that excess concrete release agent did not accumulate in the formwork.

The oil-based concrete release agent was applied as it was without dilution, and the water-based concrete release agent was diluted under the dilution conditions adopted in the above-mentioned evaluation of "emulsification stability" and applied.

As described above, the concrete material (hydraulic composition) was poured into the steel formwork using a jug in a single operation on the formwork coated with the concrete release agent on the inner surface. Then, using a table vibrator, the mold was vibrated (frequency 2800 vpm) for 30 seconds, and then allowed to stand in a constant temperature room at 20 ° C. and 80% humidity. Then, after 24 hours, the hardened concrete was removed from the formwork. After that, the inner surface of the formwork was confirmed, and the degree of adhesion of the concrete material to the formwork was visually confirmed, and the peelability was evaluated. The evaluation criteria are shown below. The evaluation results are shown in Tables 6 and 8.

S: Almost no concrete material remains on the formwork A: Concrete material adheres slightly to the formwork C: Concrete material adheres considerably to the formwork

(Surface beauty)
After evaluating the peelability, the side surface (cylindrical curved surface) of the obtained columnar hardened concrete was scanned with a handy scanner (“400-SCN032” manufactured by Sanwa Direct Co., Ltd., resolution 900 dpi), and the scanned image was edited as a bitmap image. -The binarization process was performed using the processing software "GIMP 2.10.20". The threshold value for the binarization process was set so that the number of bubble marks in the original scanned image and the number of bubble marks in the processed image were equal to each other. At that time, the formwork boundary line remaining on the hardened concrete material may be recognized as black, but this part was deleted and made white. Then, it was divided into a bubble mark recognized as black and a part other than the bubble mark recognized as white. Then, the bubble occupancy rate (that is, the ratio (%) of the portion corresponding to the bubble mark to the entire side surface of the hardened concrete which is the scanned image) was calculated. Then, the ratio of the bubble occupancy rate of each hardened concrete product to the bubble occupancy rate of the standard test product (standard product) (formula: bubble occupancy rate of each hardened concrete product / bubble occupancy rate of the standard product x 100 (%)). Was calculated and the surface aesthetics were evaluated. The evaluation criteria are shown below. The evaluation results are shown in Tables 6 and 8.

SS: When the ratio of the bubble occupancy of each concrete hardened product to the bubble occupancy of the standard product is less than 20% S: The ratio of the bubble occupancy of each concrete hardened product to the bubble occupancy of the standard product is 20% When the above is less than 30% A: When the ratio of the bubble occupancy of each concrete cured product to the bubble occupancy of the standard product is 30% or more and less than 50% B: Each concrete to the bubble occupancy of the standard product When the ratio of the bubble occupancy of the cured product is 50% or more and less than 70% C: When the ratio of the bubble occupancy of each concrete cured product to the bubble occupancy of the standard product is 70% or more.

(result)
As shown in Tables 6 and 8, by blending the auxiliary agent for concrete release agent of the present invention with the concrete release agent, the concrete release agent is excellent with the formwork in the hardened concrete material in the formwork. It was confirmed that the peelability was exhibited and the surface appearance of the obtained hardened concrete was excellent. Similarly, it was confirmed that the concrete release agent of the present invention exhibited excellent peelability from the formwork in the hardened concrete material in the formwork, and further, the surface appearance of the obtained hardened concrete material was excellent.

The auxiliary agent for a concrete release agent of the present invention can be used as an auxiliary agent to be blended in a concrete release agent that exhibits a release property between a mold and concrete or the like at the time of manufacturing concrete or the like. Further, the concrete release agent of the present invention can be used as an agent that exhibits the release property between the formwork and the concrete or the like at the time of manufacturing the concrete or the like.

Claims

An auxiliary agent for a concrete release agent, which contains the component (A) represented by the following general formula (1).

(In the general formula (1), p is 0 or an integer of 1. R 1 is a hydrocarbon group having 1 to 22 carbon atoms. R 2 is an organic group represented by −X—H (where X is). Is a (poly) oxyalkylene group formed of 1 to 30 oxyalkylene groups having 2 to 4 carbon atoms , in which case p is 0), a methyl group, or a hydrogen atom. Is an organic group represented by −Y—H (where Y is a (poly) oxyalkylene group formed by 1 to 30 oxyalkylene groups having 2 to 4 carbon atoms (in this case, p is 0). ), And the organic group is the organic group represented by -X-H or a hydrogen atom) and the organic group represented by -CH 2 - COOM 1 (provided that M 1 ). Is a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), or an organic amine, and the organic group represented by the -CH2 -COM 1 is that R 2 is a methyl group or a hydrogen atom. The total number of oxyalkylene groups represented by X and Y in R 2 and R 3 is 3 to 40).
The auxiliary agent for a concrete release agent according to claim 1, further comprising a component (B) represented by the following general formula (2).

(In the general formula (2), R 4 is a hydrocarbon group having 6 to 22 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms. R 5 O is an oxyalkylene group having 2 to 4 carbon atoms. It is a group (however, when there are a plurality of the oxyalkylene groups, it can be one kind alone or two or more kinds). M 2 is a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom). Alternatively, it is an organic amine. N is an integer of 0 to 20. M is an integer of 1 or 2.)
The component (B) contains the component (P1) having m = 1 and the component (P2) having m = 2 in the general formula (2).
In the P-nuclear NMR measurement after the alkaline overneutralization pretreatment, when the total of the P-nuclear NMR integral ratios attributed to the component (P1) and the component (P2) is 100%,
The auxiliary agent for a concrete release agent according to claim 2, wherein the P-nuclear NMR integral ratio attributed to the component (P1) is 30 to 90%.
When the total content ratio of the component (A) and the component (B) is 100 parts by mass,
The auxiliary agent for a concrete release agent according to any one of claims 2 or 3, which contains the component (A) in an amount of 1 to 99 parts by mass and the component (B) in a proportion of 1 to 99 parts by mass.
The auxiliary agent for a concrete release agent according to claim 1, further containing a component (C) which is at least one compound selected from a fatty acid having 8 to 30 carbon atoms and a salt thereof.
When the total content ratio of the component (A) and the component (C) is 100 parts by mass,
The auxiliary agent for a concrete release agent according to claim 5, which contains the component (A) in an amount of 1 to 99 parts by mass and the component (C) in a proportion of 1 to 99 parts by mass.
The auxiliary agent for a concrete release agent according to claim 2 or 3, further containing a component (C) which is at least one compound selected from a fatty acid having 8 to 30 carbon atoms and a salt thereof.
When the total content ratio of the component (A), the component (B), and the component (C) is 100 parts by mass,
The concrete peeling according to claim 7, wherein the component (A) is contained in an amount of 1 to 98 parts by mass, the component (B) is contained in an amount of 1 to 98 parts by mass, and the component (C) is contained in a ratio of 1 to 98 parts by mass. Auxiliary agent.
A concrete release agent comprising the auxiliary agent for a concrete release agent according to any one of claims 1 to 8 and a base oil.
When the total content of the concrete release agent auxiliary and the base oil is 100 parts by mass,
The concrete release agent according to claim 9, which contains 0.5 to 20 parts by mass of the auxiliary agent for a concrete release agent and 80 to 99.5 parts by mass of the base oil.
The auxiliary agent for a concrete release agent according to any one of claims 1 to 8, a base oil, and a nonionic surfactant (excluding those corresponding to the component (A)) are contained. Characteristic concrete release agent.
When the total content of the concrete release agent auxiliary, the base oil, and the nonionic surfactant is 100 parts by mass.
The concrete release agent auxiliary agent is contained in a proportion of 0.5 to 20 parts by mass.
The base oil is contained in a proportion of 60 to 98.5 parts by mass,
The concrete stripping agent according to claim 11, which contains the nonionic surfactant in a proportion of 1 to 20 parts by mass.
A coating step of applying the concrete release agent according to claim 9 or 10 to the inner surface of a concrete formwork,
The filling process of filling the formwork with the concrete forming material, which is the concrete material,
A method for producing concrete, comprising: a demolding step of demolding concrete, which is a material for forming concrete hardened in the formwork, from the formwork.
A coating step of applying the aqueous liquid of the concrete stripping agent, which is a mixture of the concrete stripping agent and water according to claim 11 or 12, to the inner surface of the concrete formwork.
The filling process of filling the formwork with the concrete forming material, which is the concrete material,
A method for producing concrete, comprising: a demolding step of demolding concrete, which is a material for forming concrete hardened in the formwork, from the formwork.