JP6901182B1 - Auxiliary agent for concrete release agent, concrete release agent and concrete manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an auxiliary agent for a concrete release agent (auxiliary agent for a concrete release agent) which is excellent in peelability and surface aesthetics and can obtain a cured concrete product in which the occurrence of color unevenness is suppressed. SOLUTION: The component (A) represented by the general formula (1) and at least one component (B) selected from the group consisting of fatty acids having 8 to 30 carbon atoms and salts thereof are contained. Auxiliary agent for concrete release agent. [Selection diagram] None

Description

The present invention relates to an auxiliary agent for a concrete release agent, a concrete release agent, and a method for producing 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, a hardened concrete product such as a concrete product has a problem that air bubble marks are generated on the surface due to air bubbles generated between the concrete product and the mold during its production. These air 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 portion is cut or the surface is embedded by applying mortar to process the surface state of the hardened concrete. There is.

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

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

However, it is a new release agent that replaces the 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 mold and bubbles of the obtained cured concrete product. There has been a demand for the development of a release agent having few marks and a good surface appearance, and further suppressing the occurrence of color unevenness (darkening) due to poor curing or the like, and an auxiliary agent blended therein.

Therefore, in view of the above circumstances, the present invention satisfactorily exhibits the peelability of the hardened concrete product from the mold by blending it with the concrete release agent, and the concrete is hardened after peeling due to bubble marks. Auxiliary agents (that is, auxiliaries for concrete release agents) that improve the surface aesthetics of objects and make it difficult for color unevenness (darkening) due to poor curing or oil stains to occur, concrete release agents and concrete containing these. The object is to provide a manufacturing method for concrete.

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

[1] The component (A) represented by the following general formula (1) and
At least one component (B) selected from the group consisting of fatty acids having 8 to 30 carbon atoms and salts thereof, and
The component (C) represented by the following general formula (2) and
Contains,
When the component (A), the component (B), and the component (C) are contained, and the total content of these components is 100 parts by mass.
The component (A) is contained in a proportion of 35 to 87 parts by mass,
The component (B) is contained in a proportion of 8 to 48 parts by mass,
An auxiliary agent for a concrete release agent, which comprises the component (C) in a proportion of 5 to 50 parts by mass.

（一般式（１）において、Ｒ^１は、炭素数６〜２４の炭化水素基、炭素数６〜２４の炭化水素アシル残基である。Ｒ^２Ｏは、炭素数２〜４のオキシアルキレン基（ただし、当該オキシアルキレン基が複数存在する場合、１種単独または２種以上とすることができる）である。Ｒ^３は、水素原子、又は炭素数１〜４の炭化水素基である。ｎは、１〜２０の整数である。）

(In the general formula (1), R ¹ is a hydrocarbon group having 6 to 24 carbon atoms and a hydrocarbon acyl residue having 6 to 24 carbon atoms. R ² O is an oxyalkylene group 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.) R ³ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Is an integer from 1 to 20.)

（一般式（２）において、Ｒ^４は、炭素数１０〜３０の炭化水素基である。Ｒ^５Ｏは、炭素数２〜４のオキシアルキレン基（ただし、当該オキシアルキレン基が複数存在する場合、１種単独または２種以上とすることができる）である。ｍは、２６〜１００の整数である。但し、一般式（２）中の−（Ｒ^５Ｏ）_ｍ−は、炭素数２〜４のオキシアルキレン基の構成割合の合計を１００モル％とすると、炭素数３のオキシアルキレン基を７０〜１００モル％の割合で有する。）

(In the general formula (2), R ⁴ is a hydrocarbon group having 10 to 30 carbon atoms. R ⁵ O is an oxyalkylene group having 2 to 4 carbon atoms (provided that a plurality of the oxyalkylene groups are present). 1 type alone or 2 types or more). M is an integer of 26 to 100. However, − (R ⁵ O) _m − in the general formula (2) has 2 carbon atoms. Assuming that the total composition ratio of the oxyalkylene groups of ~ 4 is 100 mol%, the oxyalkylene group having 3 carbon atoms is contained in the ratio of 70 to 100 mol%).

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[2] A concrete release agent containing the auxiliary agent for a concrete release agent according to the above [1] and a base oil.

[3] When the total content of the concrete release agent auxiliary and the base oil is 100 parts by mass.
The concrete release agent auxiliary agent is contained in a proportion of 0.1 to 25 parts by mass.
The concrete release agent according to the above [2], which contains the base oil in a proportion of 75 to 99.9 parts by mass.

[4] The base oil, the component (A) constituting the concrete release agent auxiliary according to the above [1], and the component (B) constituting the concrete release agent auxiliary according to the above [1]. A concrete release agent containing the above-mentioned component (C) constituting the auxiliary agent for the concrete release agent according to the above [1].
A concrete release agent containing the component (A) and the nonionic surfactant containing the component (C), the component (B), and the base oil.

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[5] When the total content of the base oil, the component (B), and the nonionic surfactant is 100 parts by mass.
The base oil is contained in a proportion of 70 to 98.95 parts by mass,
The component (B) is contained in a proportion of 0.05 to 10 parts by mass,
The concrete release agent according to the above [4], which contains the nonionic surfactant in a proportion of 1 to 20 parts by mass.

[6] A coating step of applying the concrete release agent according to the above [2] or [3] to the inner surface of a concrete formwork, and
A filling process of filling the formwork with a concrete forming material, which is a concrete material,
A method for producing concrete, which comprises a demolding step of demolding concrete, which is a material for forming concrete hardened in the formwork, from the formwork.

[7] A coating step of applying an aqueous liquid of a concrete release agent obtained by mixing the concrete release agent according to the above [4] or [5] with water to the inner surface of a concrete formwork.
A filling process of filling the formwork with a concrete forming material, which is a concrete material,
A method for producing concrete, which comprises 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 a hardened concrete product from a formwork, and bubbles in the hardened concrete product after peeling. It has the effect of making the surface aesthetically pleasing with few marks, and further making it difficult for color unevenness due to poor curing or oil bleeding to occur.

The concrete release agent of the present invention exhibits good peelability of the hardened concrete from the formwork, has few bubble marks on the hardened concrete after peeling, improves the surface appearance, and further, poor hardening, oil stains, etc. It has the effect of making it difficult for color unevenness to occur due to the above.

According to the method for producing concrete of the present invention, the hardened concrete can be satisfactorily peeled off from the mold, further, there are few bubble marks and the surface appearance is good, and it is caused by poor hardening and oil stains. This has the effect of being able to produce a hardened concrete product in which the occurrence of color unevenness is suppressed.

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 means parts by mass.

(1) Auxiliary agent for concrete release agent:
The auxiliary agent for a concrete release agent of the present invention is at least one component selected from the group consisting of the component (A) represented by the general formula (1), a fatty acid having 8 to 30 carbon atoms, and a salt thereof (a component (A). B) and. By blending such an auxiliary agent for a concrete release agent with the 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. There are few marks and the surface appearance is good, and moreover, color unevenness due to poor curing or oil bleeding is less likely to occur. In other words, in addition to the presence of air bubble marks, the hardened concrete after peeling may have color unevenness (a part that is darker than the surrounding part) due to poor curing or oil stains. According to the auxiliary agent for a concrete release agent of the present invention, not only the bubble marks can be reduced, but also the occurrence of the above-mentioned color unevenness can be suppressed. This color unevenness can also be said to be discoloration of the surface of the hardened concrete. Such surface discoloration is caused not only by the composition of the concrete forming material but also by the release agent. Suppressing the occurrence of color unevenness in this way also eliminates the poor curing of the hardened concrete product, and also makes it possible to obtain a hardened concrete product of higher quality.

(1-1) Ingredient (A):
The component (A) is a compound represented by the following general formula (1). By blending this component (A) together with the component (B), the peelability of the hardened concrete product can be improved, and further, the surface appearance of the hardened concrete product after peeling is improved. That is, it is possible to suppress the generation of air bubble marks formed between the formwork and the hardened concrete, and as a result, the durability of the hardened concrete is prevented from being lowered, and the surface portion of the hardened concrete is cut. By doing so, processing work such as eliminating air bubble marks becomes unnecessary, and productivity is improved. Furthermore, by blending the component (A) together with the component (B), the occurrence of color unevenness can be suppressed.

（一般式（１）において、Ｒ^１は、炭素数６〜２４の炭化水素基、炭素数６〜２４の炭化水素アシル残基である。Ｒ^２Ｏは、炭素数２〜４のオキシアルキレン基（ただし、当該オキシアルキレン基が複数存在する場合、１種単独または２種以上とすることができる）である。Ｒ^３は、水素原子、又は炭素数１〜４の炭化水素基である。ｎは、１〜２０の整数である。）

(In the general formula (1), R ¹ is a hydrocarbon group having 6 to 24 carbon atoms and a hydrocarbon acyl residue having 6 to 24 carbon atoms. R ² O is an oxyalkylene group 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.) R ³ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Is an integer from 1 to 20.)

^{R 1} in the general formula (1) is a hydrocarbon group having 6 to 24 carbon atoms and a hydrocarbon acyl residue having 6 to 24 carbon atoms. Among these, a hydrocarbon group having 8 to 24 carbon atoms and carbon It is preferably a hydrocarbon acyl residue of number 8-24. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent which is excellent in both peelability and surface aesthetics and can further suppress the occurrence of color unevenness.

^{Examples of R 1} in the general formula (1) include hexyl alcohol, heptyl alcohol, octyl alcohol, 2-ethyl-hexyl alcohol, nonyl alcohol, decyl alcohol, 2-propyl-heptyl alcohol, undecyl alcohol, and dodecyl alcohol. Fatty acids were removed from aliphatic alcohols having 6 to 24 carbon atoms such as 2-butyl-octyl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, eicosyl alcohol, and docosyl alcohol. Residues: Hexanoic acid, heptanic acid, capric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearyl acid, oleic acid, linoleic acid, linolenic acid, ricinolic acid, arachidic acid, behenic acid, lignoseric acid, serotic acid , Montanic acid, melicic acid, isostearic acid, erucic acid, avietic acid, tall oil fatty acid, coconut oil fatty acid, beef fat fatty acid, lanolin fatty acid, loginic acid and other carboxylic acids with 6 to 24 carbon atoms minus hydroxyl groups. And so on.

^{R 2} O in the general formula (1) 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, only an oxyalkylene group having 2 carbon atoms may be used, or a combination of an oxyalkylene group having 2 carbon atoms and another oxyalkylene group (specifically, an oxyalkylene group having 3 carbon atoms) may be used. good. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent which is excellent in both peelability and surface aesthetics and can further suppress the occurrence of color unevenness.

^{R 3} in the general formula (1) is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Among these, a hydrogen atom is preferable. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent which is excellent in both peelability and surface aesthetics and can further suppress the occurrence of color unevenness.

Although n in the general formula (1) can be an integer of 1 to 25, in the present invention, n is an integer of 1 to 20. That is, the component (A) is a compound in which n satisfies an integer of 1 to 20 in the general formula (1). More preferably, when R ¹ is a hydrocarbon acyl residue having 6 to 24 carbon atoms, n is preferably an integer of 1 to 7. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent which is excellent in both peelability and surface aesthetics and can further suppress the occurrence of color unevenness.

(1-2) Component (B):
The auxiliary agent for a concrete release agent of the present invention further contains the component (B). This component (B) is at least one compound selected from the group consisting of fatty acids having 8 to 30 carbon atoms and salts thereof. By containing the component (B) together with the component (A), it is possible to obtain an auxiliary agent for a concrete release agent which is further excellent in both peelability and surface aesthetics and can further suppress the occurrence of color unevenness. .. More specifically, the component (B), in combination with the component (A), improves the peelability between the formwork and the hardened concrete (hydraulic composition), and is further formed on the surface of the hardened concrete. Suppresses the generation of bubble marks. Furthermore, the occurrence of color unevenness on the surface of the hardened concrete can be further suppressed.

The component (B) is at least one selected from the group consisting of fatty acids having 8 to 30 carbon atoms and salts thereof, and among these, fatty acids having 8 to 24 carbon atoms and salts 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, and the effect of suppressing color unevenness may not be sufficient.

Examples of the component (B) include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinolic acid, arachidic acid, bechenic acid, lignoceric acid, and cerotic acid. , Montanic acid, melissic 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 tallow fatty acid, castor oil fatty acid, lanolin fatty acid and the like, which are mixtures thereof, and salts thereof.

In the auxiliary agent for concrete release agent of the present invention, the blending ratio of the component (A) and the component (B) is not particularly limited, but it is preferably as follows. 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 10 to 95 parts by mass, and the component (B) is contained in an amount of 5 to 90 parts by mass. It is preferable to contain in the ratio of. With such a blending ratio, it is possible to obtain an auxiliary agent for a concrete release agent, which is further excellent in both peelability and surface aesthetics and can further suppress the occurrence of color unevenness.

A more preferable blending ratio of the component (A) is 20 to 95 parts by mass, and a particularly preferable ratio is 40 to 90 parts by mass. The more preferable blending ratio of the component (B) is 5 to 80 parts by mass, and the particularly preferable ratio is 10 to 60 parts by mass.

(1-3) Component (C):
The auxiliary agent for a concrete release agent of the present invention further contains the component (C). This component (C) is a compound represented by the following general formula (2). By further containing the component (C), it is possible to obtain an auxiliary agent for a concrete release agent which is further excellent in both peelability and surface aesthetics and can further suppress the occurrence of color unevenness.

（一般式（２）において、Ｒ^４は、炭素数１０〜３０の炭化水素基である。Ｒ^５Ｏは、炭素数２〜４のオキシアルキレン基（ただし、当該オキシアルキレン基が複数存在する場合、１種単独または２種以上とすることができる）である。ｍは、２６〜１００の整数である。但し、一般式（２）中の−（Ｒ^５Ｏ）_ｍ−は、炭素数２〜４のオキシアルキレン基の構成割合の合計を１００モル％とすると、炭素数３のオキシアルキレン基を７０〜１００モル％の割合で有する。）

(In the general formula (2), R ⁴ is a hydrocarbon group having 10 to 30 carbon atoms. R ⁵ O is an oxyalkylene group having 2 to 4 carbon atoms (provided that a plurality of the oxyalkylene groups are present). 1 type alone or 2 types or more). M is an integer of 26 to 100. However, − (R ⁵ O) _m − in the general formula (2) has 2 carbon atoms. Assuming that the total composition ratio of the oxyalkylene groups of ~ 4 is 100 mol%, the oxyalkylene group having 3 carbon atoms is contained in the ratio of 70 to 100 mol%).

^{R 4} in the general formula (2) is a hydrocarbon group having 10 to 30 carbon atoms, and among these, a hydrocarbon group having 12 to 26 carbon atoms is preferable. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent which is excellent in both peelability and surface aesthetics and can further suppress the occurrence of color unevenness.

R ⁴ in the general formula (2), for example, decyl alcohol, 2-propyl - heptyl alcohol, undecyl alcohol, dodecyl alcohol, 2-butyl - octyl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, iso Residues obtained by removing hydroxyl groups from aliphatic alcohols having 10 to 30 carbon atoms such as stearyl alcohols, oleyl alcohols, eicosyl alcohols, docosyl alcohols, hexacosyl alcohols, and tricosyl alcohols can be mentioned.

^{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, only an oxyalkylene group having 3 carbon atoms may be used, or a combination of an oxyalkylene group having 3 carbon atoms and another oxyalkylene group (specifically, an oxyalkylene group having 2 carbon atoms) may be used. good. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent which is excellent in both peelability and surface aesthetics and can further suppress the occurrence of color unevenness.

M in the general formula (2) is an integer of 26 to 100. However, the general formula (2) in the - ^(R 5 _{O) m} -, when 100 mol% of the total composition ratio of oxyalkylene group having 2 to 4 carbon atoms, 70 to the oxyalkylene group having 3 carbon atoms It has a ratio of 100 mol%. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent which is excellent in both peelability and surface aesthetics and can further suppress the occurrence of color unevenness.

In the general formula (2), m is an integer of 26 to 80, and − (R ⁵ O) _m − is 100 mol%, which is the total composition ratio of the oxyalkylene group having 2 to 4 carbon atoms. Then, it is preferable to have an oxyalkylene group having 3 carbon atoms in a proportion of 75 to 100 mol%. By doing so, it is possible to obtain an auxiliary agent for a concrete release agent which is particularly excellent in both peelability and surface aesthetics and can particularly suppress the occurrence of color unevenness.

In the auxiliary agent for concrete release agent of the present invention, the compounding ratio of the component (A), the component (B), and the component (C) can be as follows. That is, when the component (A), the component (B), and the component (C) are contained and the total content of these is 100 parts by mass, the component (A) is contained in a ratio of 10 to 90 parts by mass. , The component (B) can be contained in a proportion of 1 to 80 parts by mass, and the component (C) can be contained in a proportion of 1 to 89 parts by mass. With such a blending ratio, it is possible to obtain an auxiliary agent for a concrete release agent which is particularly excellent in both peelability and surface aesthetics and can particularly suppress the occurrence of color unevenness.

The blending ratio of the component (A) can be 30 to 90 parts by mass, and in the present invention, it is 35 to 87 parts by mass. The blending ratio of the component (B) can be 5 to 50 parts by mass, which is 8 to 48 parts by mass in the present invention. Further, in the present invention, the blending ratio of the component (C) is 5 to 50 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 component (A), the component (B), and the component (C). Examples of such other components include alcohols having a hydrocarbon group having 6 to 22 carbon atoms, alcohols and phenols having an aromatic hydrocarbon group having 6 to 30 carbon atoms, alkylene oxide adducts thereof, and polyalkylenes. Examples thereof include oxides, inorganic phosphoric acid and salts thereof, water and other organic solvents.

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

(2) Concrete release agent:
The concrete release agent contains a base oil as a main agent and further contains an auxiliary agent for a concrete release 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 the purpose of use. It is used.

The above-mentioned auxiliary agent for concrete release agent of the present invention can be blended in both water-based type and oil-based type, and can improve peelability and surface aesthetics satisfactorily, and further suppress the occurrence of color unevenness. it can. That is, the above-mentioned auxiliary agent for concrete release agent of the present invention is good for both water-based type (water-based) release agent and oil-based type (oil-based) release agent. 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 0.1 to 25 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 75 to 99.9 parts by mass. By doing so, the peelability of the hardened concrete product from the formwork is further exhibited, the bubble marks on the hardened concrete product after peeling are reduced, the surface appearance is further improved, and the occurrence of color unevenness is further prevented. It can be suppressed.

A more preferable blending ratio of the auxiliary agent for a concrete release agent is 1 to 20 parts by mass, and a particularly preferable ratio is 2 to 18 parts by mass. The more preferable blending ratio of the base oil is 80 to 99 parts by mass, and the particularly preferable ratio is 82 to 98 parts by mass.

The oil-based concrete release agent may 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 the other additives may 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 includes a base oil as a main agent, a component (A) described in the above-mentioned auxiliary agent for concrete release agent of the present invention, and a component (A) described in the above-mentioned auxiliary agent for concrete release agent of the present invention ( A concrete release agent containing B), which contains a nonionic surfactant containing the component (A), the component (B), and a base oil. This water-based concrete release agent 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.

In the present invention, as the nonionic surfactant, in addition to the above-mentioned component (A), the above-mentioned component (C) described in the above-mentioned auxiliary agent for concrete release agent of the present invention is contained. By further containing this component (C), the concrete release agent is extremely excellent in both peelability and surface aesthetics, and further, the occurrence of color unevenness can be suppressed.

As the nonionic surfactant, other nonionic surfactants other than the component (A) and the component (C) can be adopted, and the other nonionic surfactants are not particularly limited and are conventionally known concrete release agents. The nonionic surfactant used in the above can be appropriately selected and adopted. For example, alkyl alcohols, alkylene alcohols, alkylphenols and their alkylene oxide adducts, mono (or di, tri) styrylphenol-alkylene oxide adducts, castor oil-alkylene oxide adducts, hardened castor oil-alkylene oxide adducts, sorbitan fatty acids. Examples thereof include an ester and an alkylene oxide adduct thereof, a (poly) glycerin fatty acid ester and an alkylene oxide adduct thereof, a sucrose fatty acid ester and an alkylene oxide adduct thereof.

This water-based concrete release agent contains 70 to 98.95 parts by mass of base oil when the total content of the base oil, component (B), and nonionic surfactant is 100 parts by mass. It is preferable that the component (B) is contained in a proportion of 0.05 to 10 parts by mass and the nonionic surfactant is contained 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 improved, the surface appearance of the hardened concrete product after peeling can be further improved, and the occurrence of color unevenness can be suppressed. ..

A more preferable blending ratio of the base oil is 79 to 94.8 parts by mass, and a particularly preferable ratio is 80 to 93.4 parts by mass. The more preferable blending ratio of the component (B) is 0.2 to 5 parts by mass, and the particularly preferable ratio is 0.6 to 5 parts by mass. The more preferable blending ratio of the nonionic surfactant is 5 to 16 parts by mass.

The water-based concrete release agent can further contain other additives in addition to the base oil, the component (B), and the nonionic surfactant (including the component (A) and the component (C)).

Examples of other additives include by-products contained in the base oil and by-products such as polyalkylene oxide generated when synthesizing a nonionic surfactant.

The content ratio of the other additives may be, for example, 1 to 10% by mass of the total amount of the 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 when producing concrete (hardened concrete). The type, material, and composition of the hardened concrete are not particularly limited. That is, it can be satisfactorily used as a release agent when peeling a cured concrete product made of a conventionally known material. The formwork is usually made of metal such as steel or wood, 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 be done.

(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. This method includes a filling step of filling the concrete forming material into the formwork and a demolding step of removing the concrete, which is the 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 used, the hardened concrete can be satisfactorily peeled from the mold, and further, there are few bubble marks and the surface appearance is good. Further, it is possible to produce a hardened concrete product in which the occurrence of color unevenness is suppressed. 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 a 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 to the inner surface of the mold is not particularly limited, and for example, spraying with a brush, spray, or the like can be adopted.

The concrete release agent is preferably applied evenly 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 adopted, the concrete release agent can be dried after being applied 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 step:
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. The aqueous liquid preparation step is a step of mixing a concrete release agent and water to prepare an aqueous liquid of the concrete release agent before the above-mentioned coating step.

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 mold 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 used.

(4-4) Curing process:
Usually, a curing process can be adopted in which the ready-mixed concrete is filled in the formwork and then the concrete is hardened. In the method for producing concrete of the present invention, the curing method until the concrete is hardened is not particularly limited, 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 demolding concrete, which is a material for forming concrete hardened in the formwork, from the formwork.

The method for removing the concrete (hardened concrete) from the mold 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 solution obtained by diluting the concrete release agent with water, the demolding of the hardened concrete product in the present demolding step becomes easy (that is, 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.

(Synthesis Example 1) Synthesis of component (A-1):
The autoclave was charged with 484.0 g of a saturated fatty alcohol having 12 to 13 carbon atoms (SAFOL23, manufactured by Sasol) and 2.1 g of a 48% potassium hydroxide aqueous solution as a catalyst. Then, the water was distilled under reduced pressure at 120 ° C. for 2 hours with stirring. Next, the inside of the autoclave was sufficiently replaced with nitrogen, and the temperature was maintained at 120 ° C., and 538.5 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 to complete the reaction. The reaction product was neutralized with 2.0 g of a 75% aqueous phosphoric acid solution, heated to 120 ° C., and the water content was distilled under reduced pressure. Then, it was treated with Kyoward 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) to adsorb and filter the catalyst to obtain a component (A-1) corresponding to the component (A).

(Synthesis Examples 2-5) Synthesis of components (A-2) to (A-4) and (A-7):
The components (A-2) to (A-4) and (A-7) corresponding to the component (A) are synthesized in the same manner as the component (A-1) except that the raw materials and the charging ratio are changed. Obtained.

(Synthesis Example 6) Synthesis of component (A-5):
An autoclave was charged with 450.0 g of isononanol (Exxal 9, manufactured by ExxonMobil) and 2.0 g of potassium hydroxide powder as a catalyst. Then, the inside of the autoclave was sufficiently replaced with nitrogen, and 906.0 g of 1,2-propylene oxide was press-fitted so as to maintain a pressure of 0.6 MPa while maintaining 135 ° C. with stirring. Then, it was aged at the temperature for 1 hour. Subsequently, 687.2 g of ethylene oxide was press-fitted at 110 ° C. so as to maintain a pressure of 0.6 MPa. Then, it was aged at the temperature for 1 hour to complete the reaction. Then, it was treated with Kyoward 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) to adsorb and filter the catalyst to obtain a component (A-5) corresponding to the component (A).

(Synthesis Examples 7-9) Synthesis of components (A-6), (A-11), (A-12):
The components (A-6), (A-11), and (A-12) corresponding to the component (A) are synthesized in the same manner as the component (A-5) except that the raw materials and the charging ratio are changed. Obtained.

(Synthesis Example 10) Synthesis of component (A-10):
500.0 g of oleic acid, 368.8 g of triethylene glycol monobutyl ether and 34.0 g of paratoluenesulfonic acid monohydrate were charged in a reaction vessel, and the reaction was carried out at 140 ° C. while stirring and distilling off water under reduced pressure. The acid value was confirmed, and when the reaction rate of oleic acid reached 99%, cooling, neutralization, and purification were carried out to obtain a component (A-10) corresponding to the component (A).

(Synthesis Example 11) Synthesis of component (C-1):
153.6 g of oleyl alcohol and 1.9 g of potassium hydroxide powder were charged into the autoclave as a catalyst. Then, the inside of the autoclave was sufficiently replaced with nitrogen, and the temperature was maintained at 110 ° C. with stirring, and 104.3 g of ethylene oxide was press-fitted so as to maintain a pressure of 0.6 MPa. Next, it was aged at the temperature for 1 hour. Then, 830.0 g of 1,2-propylene oxide was press-fitted at the temperature while maintaining a pressure of 0.6 MPa and aged for 1 hour to complete the reaction. Then, it was treated with Kyoward 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) to adsorb and filter the catalyst to obtain (C-1) corresponding to the component (C).

(Synthesis Examples 12 to 15) Synthesis of components (C-2) to (C-5):
(C-2) to (C-5) corresponding to the component (C) were obtained by synthesizing in the same manner as the component (C-1) except that the raw materials and the charging ratio were changed.

Next, the components (A), the components (B), and the components (C) constituting the auxiliary agent for the concrete release agent are shown in Tables 1 to 3 below.

^{In the column of "R 1} " in Table 1, the compounds before removing the hydroxy group are shown. ^{That is, "R 1} " in the general formula (1) is a residue obtained by removing the hydroxy group from the compound listed in the column of "R ^{1" in Table 1 above.} In Table 1, as A-1 "saturated aliphatic alcohol having 12 and 13 carbon atoms", specifically, "SAFOL23 (manufactured by Sasol Co., Ltd.)" was used. Specifically, "ISOFOL16 (manufactured by Sasol Co., Ltd.)" was used as "2-hexyl-1-decanol" of A-2. Specifically, "Exxal 9 (manufactured by ExxonMobil)" was used as the "isononanol" of A-5. In Table 1, A-8 is Softanol 30 (manufactured by Nippon Shokubai Co., Ltd.), and A-9 is Softanol 50 (manufactured by Nippon Shokubai Co., Ltd.).

In Table 3, the column "R ^4" denotes a compound before, except a hydroxy group. ^{That is, "R 4} " in the general formula (2) is a residue obtained by removing the hydroxy group from the compound listed in the column of "R ^{4" in Table 3 above.} In Table 1, as C-4 "saturated aliphatic alcohol having 12 and 13 carbon atoms", specifically, "SAFOL23 (manufactured by Sasol Co., Ltd.)" was used. As "2-decyl-1-decanol" of C-5, "ISOFOL24 (manufactured by Sasol)" was used.

Next, a predetermined amount of each component shown in Table 4 below was used to prepare an auxiliary agent for a concrete release agent.

(Examples 1-9, 21-25, 27-31, 34-37, Comparative Examples 1-9, Reference Examples 10-20, 26, 32, 33)
Next, as shown in Tables 5 and 6, each component was mixed to prepare a concrete release agent. Examples 1-9, 21-25, 27, 28, Comparative Examples 1-6, and Reference Examples 10-20, 26 in Table 5 show oil-based concrete release agents, and Example 29 in Table 6 shows. ~ 31, 34 to 37, Comparative Examples 7 to 9, and Reference Examples 32 and 33 show water-based concrete release agents. Further, in Table 6, the mass portion of "water" is the base oil, the component (A), the component (B), the component (C), and other components in the nonionic surfactant (that is, the component (A) and the component (that is, the component (A)). The mass part with respect to 100 parts by mass in total of other nonionic surfactants other than C) is shown. The water-based concrete release agent does not contain water.

The "base oils" in Tables 5 and 6 are shown in Table 8 below. Further, in Table 6, "other components" of "nonionic surfactant" are shown in Table 9 below. In Table 8, 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 following evaluation methods for each of the following evaluations (formulation stability, emulsion stability, peelability, surface aesthetics (that is, degree of bubble marks), and color unevenness (darkening)) of the prepared concrete release agent are shown below.

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

(Preparation of hydraulic composition (concrete material))
In a constant temperature room at a temperature of 20 ° C. and a humidity of 80%, a 50 L bread-type forced kneading mixer was charged with all the ingredients and admixtures shown in Table 10 under the formulation conditions shown in Table 10 and kneaded for 90 seconds. Concrete was prepared. The prepared concrete was filled in a steel mold within 15 minutes after kneading. The concrete had a concrete temperature of 21 ° C., an air amount 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 kneading 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 release agent obtained by mixing a base oil and an auxiliary agent for a concrete release 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 5 and 7.

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 in the 4th week, B: The test solution was uniform when the confirmation was performed in the 1st week after the start of standing. When the test solution is not uniform when the confirmation is performed in the week C: When the test solution is not uniform when the confirmation is performed in the first week after the start of standing.

(Emulsification stability)
50 g of the prepared concrete release agent test solution was placed in a 250 mL transparent plastic container with a lid, 200 g of tap water from Gamagori City was further 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 recognized 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 found 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 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 mold using a mug in a single operation into the mold having the concrete release agent coated 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 product was removed from the mold. After that, the inner surface of the formwork was confirmed, 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 5 and 7.

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 evaluation of peelability, the side surface (cylindrical curved surface) of the obtained columnar hardened concrete was scanned with a handy scanner (Sanwa Direct's "400-SCN032", 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. In addition, when binarizing, the boundary line of the formwork remaining on the hardened concrete material and color unevenness such as darkening due to poor curing or oil stain may be recognized as "black", but this part is Deleted it as "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 of each concrete cured product to the bubble occupancy of the reference test product (standard product) (formula: bubble occupancy of each concrete cured product / bubble occupancy of the standard product × 100 (%)) Was calculated to evaluate the surface aesthetics (that is, the degree of occurrence of bubble marks). The evaluation criteria are shown below. The evaluation results are shown in Tables 5 and 7.

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

(Color unevenness)
After the evaluation of the above "peeling property", the appearance of the obtained columnar hardened concrete including the bottom surface was visually confirmed, and the occurrence of color unevenness was evaluated. The evaluation criteria are shown below. It should be noted that this color unevenness is caused by oil stains, poor curing, etc., and is a darker part than the surroundings. This color unevenness is other than the portion caused by the bubble marks and the boundary line of the mold among those recognized as "black" in the binarization treatment in the evaluation of the surface aesthetics.
S: No color unevenness on the surface of the hardened concrete product A: Almost no color unevenness on the surface of the hardened concrete product C: No color unevenness on the surface of the hardened concrete product

(result)
As shown in Tables 5 and 7, 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 product in the formwork. It was confirmed that the peelability was exhibited, the surface appearance of the obtained cured concrete product was excellent, and the occurrence of color unevenness was suppressed. Similarly, the concrete release agent of the present invention exerts an excellent peeling action on the hardened concrete product in the formwork from the mold, further has an excellent surface appearance of the obtained hardened concrete product, and causes color unevenness. Was confirmed to be suppressed.

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 peelability 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 mold and the concrete or the like at the time of manufacturing the concrete or the like.

Claims (7)

The component (A) represented by the following general formula (1) and
At least one component (B) selected from the group consisting of fatty acids having 8 to 30 carbon atoms and salts thereof, and
The component (C) represented by the following general formula (2) and
Contains,
When the component (A), the component (B), and the component (C) are contained, and the total content of these components is 100 parts by mass.
The component (A) is contained in a proportion of 35 to 87 parts by mass,
The component (B) is contained in a proportion of 8 to 48 parts by mass,
An auxiliary agent for a concrete release agent, which comprises the component (C) in a proportion of 5 to 50 parts by mass.

(In the general formula (1), R ¹ is a hydrocarbon group having 6 to 24 carbon atoms and a hydrocarbon acyl residue having 6 to 24 carbon atoms. R ² O is an oxyalkylene group 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.) R ³ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Is an integer from 1 to 20.)

(In the general formula (2), R ⁴ is a hydrocarbon group having 10 to 30 carbon atoms. R ⁵ O is an oxyalkylene group having 2 to 4 carbon atoms (provided that a plurality of the oxyalkylene groups are present). 1 type alone or 2 types or more). M is an integer of 26 to 100. However, − (R ⁵ O) _m − in the general formula (2) has 2 carbon atoms. Assuming that the total composition ratio of the oxyalkylene groups of ~ 4 is 100 mol%, the oxyalkylene group having 3 carbon atoms is contained in the ratio of 70 to 100 mol%). A concrete release agent containing the auxiliary agent for a concrete release agent according to claim 1 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 auxiliary agent is contained in a proportion of 0.1 to 25 parts by mass.
The concrete release agent according to claim 2, which contains the base oil in a proportion of 75 to 99.9 parts by mass. The base oil, the component (A) constituting the concrete release agent auxiliary according to claim 1, the component (B) constituting the concrete release agent auxiliary according to claim 1, and claim 1. A concrete release agent containing the above-mentioned component (C) constituting the concrete release agent auxiliary agent according to the above.
A concrete release agent containing the component (A) and the nonionic surfactant containing the component (C), the component (B), and the base oil. When the total content of the base oil, the component (B), and the nonionic surfactant is 100 parts by mass,
The base oil is contained in a proportion of 70 to 98.95 parts by mass,
The component (B) is contained in a proportion of 0.05 to 10 parts by mass,
The concrete release agent according to claim 4, 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 2 or 3 to the inner surface of a concrete formwork, and
A filling process of filling the formwork with a concrete forming material, which is a concrete material,
A method for producing concrete, which comprises 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 an aqueous liquid of a concrete release agent obtained by mixing the concrete release agent according to claim 4 or 5 with water to the inner surface of a concrete formwork.
A filling process of filling the formwork with a concrete forming material, which is a concrete material,
A method for producing concrete, which comprises a demolding step of demolding concrete, which is a material for forming concrete hardened in the formwork, from the formwork.