CN114561238B

CN114561238B - Auxiliary agent for concrete release agent, and method for producing concrete

Info

Publication number: CN114561238B
Application number: CN202111389975.4A
Authority: CN
Inventors: 村松郁香; 大石卓哉; 古田章宏
Original assignee: Takemoto Oil and Fat Co Ltd
Current assignee: Takemoto Oil and Fat Co Ltd
Priority date: 2020-11-27
Filing date: 2021-11-22
Publication date: 2023-10-20
Anticipated expiration: 2041-11-22
Also published as: JP2022085591A; JP6901182B1; CN114561238A

Abstract

Provided is an auxiliary agent for a concrete release agent (auxiliary agent for a concrete release agent), which can give a concrete cured product excellent in releasability and surface appearance and suppressed in occurrence of color unevenness. The auxiliary agent for the concrete release agent comprises the following components: a component (A) represented by the general formula (1), and a component (B) of at least 1 selected from the group consisting of fatty acids having 8 to 30 carbon atoms and salts thereof.

Description

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

Technical Field

The present invention relates to an auxiliary agent for a concrete release agent, and a method for producing concrete. More specifically, the present invention relates to an additive for a concrete release agent which improves releasability and surface appearance, a concrete release agent containing the additive, and a method for producing concrete.

Background

Conventionally, concrete cured products such as concrete products have the following problems: during production, bubbles are generated on the surface due to bubbles generated between the mold frame and the mold. This bubble mark is not preferable from the viewpoints of durability and surface appearance of the concrete product. Therefore, in general, after demolding from a mold frame, a surface portion is cut or a surface-state processing operation of a concrete cured product is performed by performing an embedding operation of applying mortar to the surface.

However, since such a processing operation requires much effort and cost, a mold release agent or the like capable of suppressing generation of bubble marks on the surface of a concrete cured product has been reported (for example, refer to patent documents 1 to 3).

Prior art literature

Patent literature

Patent document 1: japanese patent application laid-open No. 2018-130957

Patent document 2: japanese patent laid-open No. 9-507181

Patent document 3: japanese patent laid-open No. 6-278120

Disclosure of Invention

Problems to be solved by the invention

However, development is required: the release agent and the auxiliary agent blended therein, which are used in place of the release agents and the like described in patent documents 1 to 3, are less in releasability from a mold frame and bubble marks and good in surface appearance of the obtained concrete cured product, and can further suppress occurrence of color unevenness (blackening) due to curing failure and the like.

In view of the above-described circumstances, an object of the present invention is to provide: the mixing of the additive with the concrete release agent makes the concrete release agent exhibit a good releasability of the concrete cured product from the mold frame, thereby making the surface of the concrete cured product after releasing due to the bubble mark beautiful, and further, it is difficult to produce an additive (i.e., an additive for the concrete release agent) having uneven color (blackening) due to poor curing, oil stains, or the like, a concrete release agent containing the additive, and a method for producing concrete.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by containing a specific component (a) and a specific component (B). According to the present invention, the following auxiliary agents for concrete release agents, and methods for producing concrete are provided.

[1] An auxiliary agent for a concrete release agent, comprising: a component (A) represented by the following general formula (1);

a component (B) of at least 1 selected from the group consisting of fatty acids having 8 to 30 carbon atoms and salts thereof; and

component (C) represented by the following general formula (2),

when the component (A), the component (B) and the component (C) are contained and the content ratio thereof is 100 parts by mass in total,

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;

the component (C) is contained in an amount of 5 to 50 parts by mass.

[ chemical formula 1]

(in the general formula (1), R ¹ Is a hydrocarbon group having 6 to 24 carbon atoms or a hydrocarbon acyl residue having 6 to 24 carbon atoms. R is R ² O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, 1 or 2 or more kinds may be used singly). R is R ³ Is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. n is an integer of 1 to 20. )

[ chemical formula 2]

(in the general formula (2), R ⁴ Is a hydrocarbon group having 10 to 30 carbon atoms. R is R ⁵ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, 1 or 2 or more kinds may be used singly). M is an integer of 26 to 100. However, when the ratio of the oxyalkylene groups having 2 to 4 carbon atoms is 100 mol% in total, - (R) in the general formula (2) ⁵ O) _m -containing an oxyalkylene group having 3 carbon atoms in a proportion of 70 to 100 mol%. )

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

[3] The concrete mold release agent according to the above [2], wherein the content ratio of the auxiliary agent for a concrete mold release agent and the base oil is 100 parts by mass in total,

contains the auxiliary agent for the concrete release agent in a proportion of 0.1 to 25 parts by mass, and

the base oil is contained in a proportion of 75 to 99.9 parts by mass.

[4] A concrete release agent comprising: a base oil, the component (A) constituting the auxiliary agent for a concrete release agent described in the above [1 ]; the component (B) constituting the auxiliary agent for a concrete mold release agent described in the above [1 ]; the component (C) constituting the auxiliary agent for a concrete mold release agent according to the above [1],

Characterized by comprising: a nonionic surfactant comprising the component (A) and the component (C), the component (B), and the base oil.

[5] The concrete release agent according to the above [4], wherein the content ratio of the base oil, the component (B) and the nonionic active agent is 100 parts by mass in total,

the base oil is contained in a proportion of 70 to 98.95 parts by mass,

the component (B) is contained in an amount of 0.05 to 10 parts by mass,

the nonionic surfactant is contained in a proportion of 1 to 20 parts by mass.

[6] A method for manufacturing concrete, comprising:

a coating step of coating the concrete release agent described in the above [2] or [3] on the inner surface of a concrete form;

a filling step of filling the mold frame with a concrete forming material as a concrete material; and

and a demolding step of demolding the concrete, which is the concrete forming material, cured in the mold frame from the mold frame.

[7] A method for manufacturing concrete, comprising:

a coating step of coating an aqueous solution of the concrete release agent obtained by mixing the concrete release agent described in the above [4] or [5] with water on the inner surface of a concrete form;

Effects of the invention

By mixing the auxiliary agent for a concrete release agent of the present invention into a concrete release agent, the following effects can be produced: the concrete release agent exhibits good releasability of the concrete cured product from the mold frame, and the released concrete cured product has few bubble marks and good surface appearance, and is difficult to generate uneven color caused by poor curing, greasy dirt and the like.

The concrete release agent of the invention has the following effects: the mold release property of the concrete cured product from the mold frame is well exerted, bubble marks in the concrete cured product after the mold release are less, the surface is attractive, and color unevenness caused by poor curing, greasy dirt and the like is difficult to generate.

According to the method for manufacturing concrete of the present invention, the following effects are produced: the cured concrete product can be released from the mold well, and further a cured concrete product having few bubble marks, good surface appearance and suppressed occurrence of color unevenness due to poor curing or oil stains can be produced.

Detailed Description

Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. Accordingly, it should be understood that the following embodiments may be appropriately modified, improved, etc. based on conventional knowledge of those skilled in the art without departing from the spirit of the present invention. In the following examples and the like, "%" means "% by mass" and "parts" means "parts by mass" unless otherwise noted.

(1) Auxiliary agent for concrete release agent:

the auxiliary agent for the concrete release agent comprises: a component (A) represented by the general formula (1), and a component (B) of at least 1 selected from the group consisting of fatty acids having 8 to 30 carbon atoms and salts thereof. By mixing such an auxiliary agent for a concrete release agent with the concrete release agent, the concrete release agent exhibits excellent releasability of the concrete cured product from the mold frame, the bubble mark in the concrete cured product after releasing is small, the surface is beautiful, and color unevenness due to poor curing, oil stain, or the like is less likely to occur. That is, in the concrete cured product after the release, in addition to the presence of the bubble mark, color unevenness (a portion having a darker color than the surrounding portion) may occur due to curing failure, oil stain, or the like, but according to the auxiliary agent for a concrete release agent of the present invention, not only the bubble mark can be reduced, but also the occurrence of the color unevenness can be suppressed. The color unevenness can be said to be a discoloration of the surface of the concrete cured product. Such surface discoloration is caused not only by the composition of the material for forming concrete but also by the release agent. In this way, suppression of occurrence of color unevenness eliminates curing failure of the concrete cured product, and thus a higher quality concrete cured product can be obtained.

(1-1) component (A):

the component (A) is a compound represented by the following general formula (1). By mixing the component (a) with the component (B), the releasability of the concrete cured product can be improved, and the surface appearance of the concrete cured product after releasing can be further improved. That is, the occurrence of bubble marks formed between the mold frame and the concrete cured product can be suppressed, and as a result, the durability of the concrete cured product is prevented from decreasing, and the processing operation for eliminating bubble marks and the like is unnecessary by cutting or the like the surface portion of the concrete cured product, thereby improving the productivity. Further, by mixing the component (a) and the component (B) together, the occurrence of color unevenness can be suppressed.

[ chemical formula 3]

(in the general formula (1), R ¹ Is a hydrocarbon group having 6 to 24 carbon atoms or a hydrocarbon acyl residue having 6 to 24 carbon atoms. R is R ² O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, 1 or 2 or more kinds may be used singly). R is R ³ Is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. n is an integer of 1 to 20。)

R of the general formula (1) ¹ Is a hydrocarbon group having 6 to 24 carbon atoms or a hydrocarbon acyl residue having 6 to 24 carbon atoms, or a hydrocarbon group having 8 to 24 carbon atoms or a hydrocarbon acyl residue having 8 to 24 carbon atoms. In this way, an auxiliary agent for a concrete release agent which is excellent in both releasability and surface appearance and can further suppress the occurrence of color unevenness can be obtained.

R as in the general formula (1) ¹ Examples include: residues after removal of hydroxyl groups from aliphatic alcohols having 6 to 24 carbon atoms such as hexanol, heptanol, octanol, 2-ethyl-hexanol, nonanol, decanol, 2-propyl-heptanol, undecanol, dodecanol, 2-butyl-octanol, tridecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, eicosyl alcohol, and eicosiol; acyl residues after removal of hydroxyl groups from carboxylic acids having 6 to 24 carbon atoms such as caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, isostearic acid, erucic acid, abietic acid, tall oil fatty acid, coco fatty acid, tallow fatty acid, lanolin fatty acid, and abietic acid.

R in the general formula (1) ² O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, 1 or 2 or more of them may be used alone, or among them, only an oxyalkylene group having 2 carbon atoms 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. In this way, an auxiliary agent for a concrete release agent which is excellent in both releasability and surface appearance and can further suppress the occurrence of color unevenness can be obtained.

R in the general formula (1) ³ Is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Among these, a hydrogen atom may be mentioned. In this way, an auxiliary agent for a concrete release agent which is excellent in both releasability and surface appearance and can further suppress the occurrence of color unevenness can be obtained.

N in the general formula (1) may be an integer of 1 to 25, and in the present invention, n is an integer of 1 to 20. That is, the component (A) is a compound satisfying the general formula (1) in which n is an integer of 1 to 20. More preferably, when R ¹ When the hydrocarbon acyl residue has 6 to 24 carbon atoms, n is preferably an integer of 1 to 7. In this way, an auxiliary agent for a concrete release agent which is excellent in both releasability and surface appearance and can further suppress the occurrence of color unevenness can be obtained.

(1-2) component (B):

the auxiliary agent for a concrete release agent of the present invention further contains component (B). The component (B) is a compound of at least 1 selected from the group consisting of fatty acids having 8 to 30 carbon atoms and salts thereof. Since the component (B) is contained together with the component (a), an auxiliary agent for a concrete release agent which is more excellent in both releasability and surface appearance and can further suppress the occurrence of color unevenness can be obtained. More specifically, the component (B) and the component (A) together improve the releasability of the mold frame from the concrete cured product (hydraulic composition) and suppress the occurrence of the bubble mark formed on the surface of the concrete cured product. Further, the occurrence of color unevenness generated on the surface of the concrete cured product can be further suppressed.

The component (B) is at least 1 selected from the group consisting of fatty acids having 8 to 30 carbon atoms and salts thereof, and among them, fatty acids having 8 to 24 carbon atoms and salts thereof are preferable, and fatty acids having 8 to 22 carbon atoms and salts thereof are preferable. When the number of carbon atoms is less than 8, the improvement effect of releasability and surface appearance, and the suppression effect of color unevenness may be insufficient.

Examples of the component (B) include: caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, isostearic acid, erucic acid, 12-hydroxystearic acid, and the like, and salts thereof, and the like. Further, there may be mentioned: tall oil fatty acids, coconut oil fatty acids, tallow fatty acids, castor oil fatty acids, lanolin fatty acids, and the like as mixtures thereof, and salts thereof.

In the auxiliary agent for a concrete release agent of the present invention, the mixing ratio of the component (a) and the component (B) is not particularly limited, but is preferably as follows. That is, when the content ratio of the component (a) and the component (B) is 100 parts by mass in total, it is preferable that the component (a) is contained in a proportion of 10 to 95 parts by mass and the component (B) is contained in a proportion of 5 to 90 parts by mass. By setting the mixing ratio as described above, an auxiliary agent for a concrete release agent which is more excellent in both releasability and surface appearance and can further suppress the occurrence of color unevenness can be obtained.

The more preferable mixing ratio of the component (A) is 20 to 95 parts by mass, and the particularly preferable ratio is 40 to 90 parts by mass. The more preferable mixing 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 component (C). The component (C) is a compound represented by the following general formula (2). By further containing the component (C), an auxiliary agent for a concrete release agent which is more excellent in both releasability and surface appearance and can further suppress the occurrence of color unevenness can be obtained.

[ chemical formula 4]

(in the general formula (2), R ⁴ Is a hydrocarbon group having 10 to 30 carbon atoms. R is R ⁵ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, 1 or 2 or more kinds may be used alone). m is an integer of 26 to 100. However, when the ratio of the oxyalkylene groups having 2 to 4 carbon atoms is 100 mol%, the- (R) in the formula (2) ⁵ O) _m -an oxyalkylene group having 3 carbon atoms in a proportion of 70 to 100 mole%. )

R in the general formula (2) ⁴ Is a hydrocarbon group having 10 to 30 carbon atoms, and among them, may be carbon A hydrocarbon group having 12 to 26 atoms. In this way, an auxiliary agent for a concrete release agent which is excellent in both releasability and surface appearance and can further suppress the occurrence of color unevenness can be obtained.

R in the general formula (2) ⁴ Examples include: residues after removal of hydroxyl groups from aliphatic alcohols having 10 to 30 carbon atoms such as decanol, 2-propyl-heptanol, undecanol, dodecanol, 2-butyl-octanol, tridecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, eicosyl alcohol, behenyl alcohol, hexacosyl alcohol, and tridecyl alcohol.

R in the general formula (2) ⁵ O is an oxyalkylene group having 2 to 4 carbon atoms (however, when a plurality of the oxyalkylene groups are present, 1 or 2 or more of them may be used alone, and among them, only an oxyalkylene group having 3 carbon atoms 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. In this way, an auxiliary agent for a concrete release agent which is excellent in both releasability and surface appearance and can further suppress the occurrence of color unevenness can be obtained.

M in the general formula (2) is an integer of 26 to 100. However, when the ratio of the oxyalkylene groups having 2 to 4 carbon atoms is 100 mol%, the- (R) in the formula (2) ⁵ O) _m -an oxyalkylene group having 3 carbon atoms in a proportion of 70 to 100 mole%. In this way, an auxiliary agent for a concrete release agent which is excellent in both releasability and surface appearance and can further suppress the occurrence of color unevenness can be obtained.

In the general formula (2), m is an integer of 26 to 80, and when the constituent ratio of the oxyalkylene groups having 2 to 4 carbon atoms is 100 mol%, R ⁵ O) _m Preferably, the alkylene oxide having 3 carbon atoms is contained in an amount of 75 to 100 mol%. In this way, an auxiliary agent for a concrete release agent which is particularly excellent in both releasability and surface appearance and is particularly capable of suppressing occurrence of color unevenness can be obtained.

In the auxiliary agent for a concrete mold release agent of the present invention, the mixing ratio of the component (a), the component (B), and the component (C) may be set as follows. That is, the component (A), the component (B) and the component (C) are contained, and the component (A) may be contained in an amount of 10 to 90 parts by mass, the component (B) may be contained in an amount of 1 to 80 parts by mass, and the component (C) may be contained in an amount of 1 to 89 parts by mass, when the total content thereof is 100 parts by mass. By setting the mixing ratio as described above, an auxiliary agent for a concrete release agent which is particularly excellent in both releasability and surface appearance and can particularly suppress occurrence of color unevenness can be obtained.

The mixing ratio of the component (a) may be 30 to 90 parts by mass, and in the present invention, 35 to 87 parts by mass. The mixing ratio of the component (B) may be 5 to 50 parts by mass, and in the present invention, 8 to 48 parts by mass. In the present invention, the mixing 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 of 6 to 22 carbon atoms, alcohols having an aromatic hydrocarbon group of 6 to 30 carbon atoms, phenols and alkylene oxide adducts thereof, polyalkylene oxides, inorganic phosphoric acids and salts thereof, water, other organic solvents, and the like.

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

(2) And (3) a 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 or the like as an additive. Such a concrete release agent has an aqueous release agent and an oily release agent, and these may be appropriately selected and used according to the concrete material and the purpose of use.

The auxiliary agent for a concrete release agent of the present invention can be mixed with either of the aqueous type and the oily type, and can improve the releasability and the surface appearance satisfactorily, and can suppress the occurrence of color unevenness. That is, the auxiliary agent for a concrete release agent of the present invention can favorably employ both aqueous (aqueous substance) release agents and oily (oily substance) release agents.

Hereinafter, the oil-type concrete release agent and the aqueous-type concrete release agent in the present invention will be described, respectively.

(2-1) oily concrete mold release agent:

the oily concrete release agent contains the base oil as a main agent and the auxiliary agent for a concrete release agent of the present invention, and is used as it is without being mixed with water when used.

The base oil is not particularly limited, and one used in a conventionally known concrete release agent can be appropriately selected and used. For example, it is possible to list: mineral oils such as lamp oil, light oil, spin oil, transformer oil, and engine oil; synthetic oils such as polyalphaolefins and polyol esters; vegetable oils such as rapeseed, coconut, palm, soybean, sesame oil, etc.; grease; fatty acid esters, and the like. Among them, at least 1 selected from the group consisting of mineral oil, synthetic oil and vegetable oil is preferable.

When the content ratio of the auxiliary agent for a concrete release agent and the base oil is 100 parts by mass, it is preferable that the oily type concrete release agent contains the auxiliary agent for a concrete release agent in a proportion of 0.1 to 25 parts by mass and the base oil in a proportion of 75 to 99.9 parts by mass. In this way, the mold releasability of the concrete cured product from the mold frame is further improved, the bubble mark in the concrete cured product after the mold release is reduced, the surface appearance is more excellent, and the occurrence of color unevenness can be further suppressed.

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

The oily type 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 the other additives include: byproducts contained in the base oil, and the like.

The content of the other additive may be, for example, 0 to 10% by mass of the entire oily concrete mold release agent.

(2-2) aqueous concrete mold release agent:

the aqueous concrete release agent is a concrete release agent containing a base oil as a main agent, the component (a) described in the auxiliary agent for a concrete release agent of the present invention, and the component (B) described in the auxiliary agent for a concrete release agent of the present invention, and contains a nonionic surfactant containing the component (a), the component (B), and the base oil. The water-based concrete release agent is added with water on site or diluted with water in advance for use.

The base oil is not particularly limited, and the same base oil as the base oil mixed in the above-mentioned oily concrete mold release agent can be appropriately selected and used.

In the present invention, the nonionic surfactant contains, in addition to the component (a), the component (C) described in the auxiliary agent for a concrete release agent of the present invention. By further containing the component (C), the concrete release agent is excellent in both releasability and surface appearance, and can suppress occurrence of color unevenness.

The nonionic surfactant is not particularly limited, and other nonionic surfactants other than the component (a) and the component (C) may be used, and nonionic surfactants used in conventionally known concrete release agents may be appropriately selected and used. For example, there may be mentioned: alkyl alcohols, alkylene alcohols, alkylphenols and alkylene oxide adducts thereof, mono (or di, tri) styrylphenol-alkylene oxide adducts, castor oil-alkylene oxide adducts, hydrogenated castor oil-alkylene oxide adducts, sorbitan fatty acid esters and alkylene oxide adducts thereof, (poly) glycerin fatty acid esters and alkylene oxide adducts thereof, sucrose fatty acid esters and alkylene oxide adducts thereof, and the like.

When the content ratio of the base oil, the component (B), and the nonionic active agent is 100 parts by mass, it is preferable that the aqueous concrete release agent contains the base oil in a ratio of 70 to 98.95 parts by mass; the component (B) is contained in an amount of 0.05 to 10 parts by mass; the nonionic surfactant is contained in a proportion of 1 to 20 parts by mass. In this way, the releasability of the concrete cured product from the mold frame can be further exhibited satisfactorily, the surface of the concrete cured product after the release is more beautiful, and the occurrence of color unevenness can be suppressed.

The more preferable mixing ratio of the base oil is 79 to 94.8 parts by mass, and the particularly preferable ratio is 80 to 93.4 parts by mass. The more preferable mixing 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. Further, the mixing ratio as the nonionic active agent is more preferably 5 to 16 parts by mass.

The aqueous concrete release agent may further contain other additives in addition to the base oil, the component (B), and the nonionic active agent (containing the component (a) and the component (C)).

Examples of the other additives include: byproducts contained in the base oil, and byproducts such as polyalkylene oxide generated during the synthesis of the nonionic surfactant.

The content of the other additive may be, for example, 1 to 10% by mass of the entire aqueous concrete mold release agent.

(3) Use of a concrete release agent:

the concrete release agent of the present invention can be used as a release agent for releasing a concrete cured product from a mold frame at the time of producing concrete (concrete cured product). The kind, material and composition of the concrete cured product are not particularly limited. That is, the composition can be suitably used as a release agent for releasing a concrete cured product made of a conventionally known material. The mold frame may be made of metal such as steel, or wooden, but the material of the mold frame is not limited, and the mold frame may be coated with the concrete mold release agent of the present invention.

(4) The manufacturing method of the concrete comprises the following steps:

the method for producing concrete of the present invention comprises the steps of: a coating step of coating the inner surface of the concrete form with the concrete release agent of the present invention or an aqueous solution obtained by diluting the agent with water; a filling step of filling a mold frame with a concrete forming material as a concrete material; and a demolding step of demolding the concrete, which is cured in the mold frame, as a material for forming the concrete from the mold frame. According to such a production method, since the concrete mold release agent of the present invention is used, the concrete cured product can be released from the mold satisfactorily, and further, the concrete cured product can be produced with few bubble marks, good surface appearance and suppressed occurrence of color unevenness. The material for forming concrete is not yet cured concrete (ready-mixed concrete).

(4-1) coating step:

the form for concrete is not particularly limited, and a form for concrete known in the prior art can be suitably used. The mold frame may be made of metal such as steel, wood, or synthetic resin.

The method of applying the concrete release agent to the inner surface of the mold frame is not particularly limited, and a spraying method such as brushing or spraying may be used.

Preferably, the concrete mold release agent is uniformly coated on the entire inner surface of the mold frame. The thickness of the coating layer of the concrete release agent is not particularly limited, and may be appropriately set.

When an aqueous concrete release agent is used, the concrete release agent may be dried after coating the inner surface of the mold frame before filling the ready-mixed concrete. The drying conditions are not particularly limited and may be appropriately set.

(4-2) an aqueous liquid preparation step:

when an aqueous concrete release agent is used, the method for producing concrete of the present invention may further include an aqueous liquid production step. The aqueous solution preparation step is a step of mixing the concrete release agent with water to prepare an aqueous solution of the concrete release agent before the coating step.

As the nonionic surfactant, the above nonionic surfactant can be suitably used.

The proportion of the concrete release agent in the aqueous solution of the concrete release agent is not particularly limited, and may be appropriately set, for example, about 1 to 99 mass%. Preferably 10 to 99 mass%. If the proportion of the concrete release agent is too small, the releasability may be lowered.

When an oily concrete release agent is used, the oily concrete release agent may be directly applied to the inner surface of the mold frame.

(4-3) filling procedure:

the method of filling the mold frame with the ready-mixed concrete is not particularly limited, and a method of injecting the ready-mixed concrete into the mold frame by a single operation or the like may be employed. After filling, the material may be tamped using a bar-shaped vibrator, a frame vibrator, or the like.

The concrete forming material (hydraulic composition) used as the concrete material is not particularly limited, and conventionally known concrete materials (hydraulic compositions) can be suitably used.

(4-4) curing procedure:

in general, a curing process of curing the concrete after filling the ready-mixed concrete in the mold frame may be employed. In the method for producing concrete of the present invention, the curing method for curing the concrete is not particularly limited, and conventionally known methods can be suitably employed. For example, the concrete-filled form may be cured by directly exposing it to an outdoor temperature, or the curing time may be shortened by heating it at about 30 to 120 ℃ for a desired time using steam, an autoclave, or the like.

(4-5) demolding procedure:

the method for producing concrete according to the present invention further comprises a demolding step of demolding the concrete as a material for forming concrete, which is cured in the mold frame, from the mold frame.

The method for releasing concrete (concrete cured product) from the mold frame is not particularly limited, and conventionally known methods can be suitably employed. In the present invention, the use of the concrete mold release agent of the present invention or an aqueous solution obtained by diluting the agent with water facilitates the release of the concrete cured product in the present release step (i.e., improves the releasability).

Examples

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):

484.0g of a saturated aliphatic alcohol having 12 to 13 carbon atoms (SAFOL 23, product of Seattle Co., ltd.) and 2.1g of a 48% aqueous potassium hydroxide solution as a catalyst were charged into the autoclave. Then, the water was distilled under reduced pressure at 120℃for 2 hours while stirring. Next, the autoclave was sufficiently replaced with nitrogen, maintained at 120℃and 538.5g of ethylene oxide was pressed in to maintain the pressure at 0.6MPa. Then, the reaction was completed by aging at this temperature for 0.5 hours. To the reaction was added 2.0g of 75% phosphoric acid aqueous solution for neutralization, the temperature was raised to 120℃and the water was distilled under reduced pressure. Then, the resultant was treated with Kyowa 600 (manufactured by Kagaoward Co., ltd.) to adsorb a catalyst and filtered to obtain a component (A-1) corresponding to the component (A).

(Synthesis examples 2 to 5) Synthesis of Components (A-2) to (A-4) and (A-7):

the synthesis was performed in the same manner as the component (A-1) except that the raw materials and the addition ratio were changed, whereby components (A-2) to (A-4) and (A-7) corresponding to the component (A) were obtained.

Synthesis example 6 Synthesis of component (A-5):

450.0g of isononanol (Exxal 9, from the company of the end-cap company) and 2.0g of potassium hydroxide powder as a catalyst were added to the autoclave. Then, the inside of the autoclave was sufficiently replaced with nitrogen gas, which was maintained at 135℃while stirring, and 906.0g of 1, 2-epoxypropane was simultaneously pressurized to maintain the pressure at 0.6MPa. Then, the mixture was cured at this temperature for 1 hour. Next, the temperature was maintained at 110℃and 687.2g of ethylene oxide was pressed in to maintain the pressure at 0.6MPa. Then, the reaction was completed by aging at this temperature for 1 hour. Then, the resultant mixture was treated with Kyoward 600 (manufactured by the company of the chemical industry, ltd.) to adsorb a catalyst and filtered, thereby obtaining component (a-5) corresponding to component (a).

(Synthesis examples 7 to 9) Synthesis of Components (A-6), (A-11) and (A-12):

the synthesis was performed in the same manner as the component (A-5) except that the raw materials and the addition ratio were changed, whereby components (A-6), (A-11) and (A-12) corresponding to the component (A) were obtained.

Synthesis example 10 Synthesis of component (A-10):

500.0g of oleic acid, 368.8g of triethylene glycol monobutyl ether, and 34.0g of p-toluenesulfonic acid monohydrate were charged into a reaction vessel, and water was removed by stirring and distillation under reduced pressure while carrying out a reaction at 140 ℃. When the acid value was confirmed and the reaction rate of oleic acid reached 99%, cooling, neutralization and purification were carried out to obtain component (A-10) corresponding to component (A).

Synthesis example 11 Synthesis of component (C-1):

153.6g of oleyl alcohol and 1.9g of potassium hydroxide powder as catalyst were charged into the autoclave. Then, the autoclave was sufficiently replaced with nitrogen gas, which was maintained at 110℃while stirring, and 104.3g of ethylene oxide was pressurized to maintain the pressure at 0.6MPa. Next, the mixture was aged at this temperature for 1 hour. Then, 830.0g of 1, 2-propylene oxide was introduced thereinto under pressure of 0.6MPa at this temperature, and the mixture was cured for 1 hour to complete the reaction. Then, the resultant was treated with Kyowa 600 (manufactured by Kagaku and chemical Co., ltd.) to adsorb a catalyst and filtered, thereby obtaining (C-1) corresponding to the component (C).

(Synthesis examples 12 to 15) Synthesis of Components (C-2) to (C-5):

synthesis was performed in the same manner as in component (C-1) except that the raw materials and the addition ratio were changed, whereby (C-2) to (C-5) corresponding to component (C) were obtained.

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

TABLE 1

In Table 1, "R ¹ The column indicates the compound prior to removal of the hydroxyl group. Namely, "R" in the general formula (1) ¹ "R is from Table 1 above ¹ "residue after removal of hydroxyl group" in the compound described in column. In Table 1, "saturated aliphatic alcohols having 12 and 13 carbon atoms" of A-1 specifically used are "SAFOL23 (from Twill Co., ltd.). Specifically, "isool 16 (ex sosolo corporation)" is used as "2-hexyl-1-decanol" of a-2. Specifically, "Exxal 9 (from the company Pratense) is used as" isononanol "of A-5. In Table 1, A-8 is softanol 30 (manufactured by Japanese catalyst Co., ltd.), and A-9 is softanol 50 (manufactured by Japanese catalyst Co., ltd.).

TABLE 2

Component (B)	Component name
		B-1	Oleic acid
B-2	Tall oil fatty acid
		B-3	Lauric acid
B-4	Isostearic acid
		B-5	Octanoic acid
B-6	Erucic acid

TABLE 3

In Table 3, "R ⁴ The column "shows the compounds prior to removal of the hydroxyl groups. Namely, "R" in the general formula (2) ⁴ "R is from the above Table 3 ⁴ The residue after removal of the hydroxyl group in the compound described in column. In Table 1, "saturated aliphatic alcohols having 12 and 13 carbon atoms" of C-4 are specifically referred to as "SAFOL23 (from Twill Co., ltd."). "2-decyl-1-tetradecanol" of C-5 is "ISOFOL 24 (manufactured by Poplar corporation)".

Next, using predetermined amounts of each component shown in table 4 below, an auxiliary agent for a concrete release agent was prepared.

TABLE 4

(examples 1 to 9, 21 to 25, 27 to 31, 34 to 37, comparative examples 1 to 9, reference examples 10 to 20, 26, 32, 33)

Next, as shown in tables 5 and 6, the components were mixed to prepare a concrete release agent. Examples 1 to 9, 21 to 25, 27, and 28, comparative examples 1 to 6, and reference examples 10 to 20, and 26 in table 5 show oil-based concrete release agents, and examples 29 to 31, 34 to 37, comparative examples 7 to 9, and reference examples 32 and 33 in table 6 show aqueous concrete release agents. In table 6, the mass parts of "water" represent the mass parts of the base oil, the component (a), the component (B), the component (C), and the other components in the nonionic surfactant (i.e., the nonionic surfactant other than the component (a) and the component (C)) in total of 100 mass parts. The aqueous concrete release agent does not contain water.

TABLE 5

TABLE 6

TABLE 7

The "base oils" in tables 5 and 6 are shown in Table 8. Further, "other components" of the "nonionic surfactant" in table 6 are shown in the following table 9. In table 8, the tattoo 32 and the sardine D are コ from petroleum, and the sardine U-46 is JXTG tattoo from tattoo. Furthermore, they are all spin oils.

TABLE 8

TABLE 9

(evaluation test)

The following evaluation methods (preparation stability, emulsion stability, releasability, surface appearance (i.e., the degree of bubble mark), and color unevenness (blackening)) were used for each of the produced concrete release agents.

In order to evaluate the "releasability", "surface appearance", and "color unevenness", a hydraulic composition (concrete material) was prepared as follows.

(preparation of hydraulic composition (concrete Material))

In a constant temperature chamber having a temperature of 20℃and a humidity of 80%, all the components and the admixture shown in Table 10 were fed into a 50L disc type forced kneading machine at once under the mixing conditions described in Table 10, and kneaded for 90 seconds, thereby preparing concrete. The prepared concrete was kneaded and then filled into a steel mold in 15 minutes. The concrete was at 21℃and 5.0% air and 18.0cm slump.

As the admixture, a high-performance water reducing agent (JIS a 6204) of 0.7 mass% relative to cement, and an AE agent (AE-300 (JIS a 6204) of 0.0025 mass% relative to cement) were used as part of kneading water.

The specific content of the materials used is as follows.

And (3) cement: ordinary portland cement (equal amount of mixture manufactured by Pacific Cement Co., ltd., mitsubishi Cement Co., ltd., sumitomo Osaka cement Co., ltd.) has a density of 3.16g/cm ³

Water: pu Jun tap water

Fine aggregate: dajing river system Liu Sha density 2.58g/cm ³

Coarse aggregate: macadam density of 2.68g/cm produced by Kawasaki ³

TABLE 10

(stability of formulation)

The test solution as a concrete release agent obtained by mixing the base oil with an auxiliary agent for a concrete release agent and the like was added to a 250mL plastic container with a cover, and then allowed to stand at 20 ℃.

Then, the state of the test liquid in the standing state was visually confirmed and evaluated as appropriate (specifically, 1 st, 2 nd and 4 th weeks after the start of the standing). The evaluation criteria are shown below. The evaluation results are shown in tables 5 and 7.

S: after the start of the standing, when the test liquid was confirmed at week 4, it was confirmed that the test liquid was uniform

A: after the start of the standing, the test solution was uniform at the time of the confirmation at week 2, but was not uniform at the time of the confirmation at week 4

B: after the start of the standing, the test solution was uniform at the time of the confirmation at week 1, but was not uniform at the time of the confirmation at week 2

C: after the start of the standing, the test solution was not uniform when the test solution was confirmed at week 1

(emulsion stability)

To a 250mL plastic container with a transparent cover, 50g of the prepared test solution as a concrete release agent was added, 200g of Pu Jun city tap water was further added, and the mixture was stirred and mixed thoroughly, and the mixture was allowed to stand at 20 ℃.

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

S: after the start of the standing, when the test liquid was confirmed at 12 hours, the test liquid was confirmed to be uniformly emulsified and clouded

A: after the start of the standing, the test solution was confirmed to be uniformly emulsified and cloudy at 6 hours, but the test solution was not observed to be uniformly emulsified and cloudy at 12 hours

B: after the start of the standing, the test solution was confirmed to be uniformly emulsified and cloudy at 1 hour, but the test solution was not observed to be uniformly emulsified and cloudy at 6 hours

C: after the start of the standing, no uniform emulsification and cloudiness of the test solution were observed when the test solution was confirmed at 1 hour

(mold release Property)

The prepared concrete mold release agent was uniformly coated on the entire inner surface of a bottomed cylindrical steel mold frame having an inner diameter of 10cm and a height of 20cm using a brush. Then, the concrete mold was left standing in a state with the bottom face turned upside down for 1 hour or more, and no excess concrete mold release agent was accumulated in the mold frame.

The oily concrete release agent was directly applied without dilution, and the aqueous concrete release agent was diluted under the dilution conditions used in the evaluation of the "emulsion stability" described above, and then applied.

As described above, in the mold frame having the concrete mold release agent coated on the inner surface, the concrete material (hydraulic composition) was poured into the steel mold frame by one-time operation using the large cup with the stem. Then, after vibration (frequency: 2800 vpm) was applied to the mold frame for 30 seconds using a table vibrator, the mold was allowed to stand in a constant temperature chamber at 20℃and a humidity of 80%. Then, the concrete cured product was released from the mold after 24 hours. Then, the inner surface of the mold frame was checked, and adhesion of the concrete material to the mold frame was visually checked, whereby releasability was evaluated. The evaluation criteria are shown below. The evaluation results are shown in tables 5 and 7.

S: almost no residual concrete material is left on the mould frame

A: the mould frame is slightly adhered with concrete material

C: the mould frame is attached with a considerable amount of concrete material

(surface beauty)

After the releasability was evaluated, the side surface (cylindrical curved surface) of the obtained cylindrical concrete cured product was scanned by a hand scanner ("400-SCN 032" manufactured by dydronate corporation, resolution 900 dpi), and the scanned image was binarized by bitmap image editing/processing software "GIMP2.10.20". The threshold value at the time of performing the binarization processing is set so that the number of bubble marks of the original scan image is equal to the number of bubble marks of the processed image. In the case of binarizing, the boundary line of the mold frame in which the concrete cured product remains and the color unevenness such as black spots due to poor curing or oil stains may be recognized as "black", but the portion is deleted to become "white". Then, the bubble mark identified as black and the portion other than the bubble mark identified as white are distinguished.

Then, the bubble occupancy (i.e., the proportion (%) of the portion corresponding to the bubble mark to the entire side surface of the concrete cured product as a scanned image) was calculated. Then, the ratio of the air bubble occupancy of each concrete cured product to the air bubble occupancy of a test article (standard article) as a standard (formula: air bubble occupancy of each concrete cured product/air bubble occupancy of the standard article. Times.100 (%)) was calculated, and the surface appearance (i.e., the degree of occurrence of air bubble mark) was evaluated. The evaluation criteria are shown below. The evaluation results are shown in tables 5 and 7.

S: the ratio of the air bubble occupancy of each concrete cured product to the air bubble occupancy of the reference product is less than 30%

A: the ratio of the air bubble occupancy of each concrete cured product to the air bubble occupancy of the reference product is 30% or more and less than 50%

B: the ratio of the air bubble occupancy of each concrete cured product to the air bubble occupancy of the reference product is 50% or more and less than 70%

C: the ratio of the air bubble occupancy of each concrete cured product to the air bubble occupancy of the reference product is 70% or more

(color unevenness)

After the above-mentioned evaluation of "releasability", the appearance including the bottom surface of the obtained columnar concrete cured product was visually confirmed, and the occurrence of color unevenness was evaluated. The evaluation criteria are shown below. The uneven color is caused by oil stains, poor curing, or the like, and is a darker portion than the surrounding area. The color unevenness is a portion other than a portion caused by a boundary line between a bubble mark and a mold frame, among portions identified as "black" when the binarization processing is performed in the evaluation of the surface appearance.

S: no color unevenness was observed at all on the surface of the concrete cured product

A: hardly any color unevenness was observed on the surface of the concrete cured product

C: considerable color unevenness was observed on the surface of the concrete cured product

(results)

As shown in table 5 and table 7, it was confirmed that: by mixing the auxiliary agent for a concrete release agent of the present invention with the concrete release agent, the concrete release agent exhibits excellent releasability between the cured concrete product in the mold frame and the mold frame, and the obtained cured concrete product has excellent surface appearance and can suppress occurrence of color unevenness. Likewise, it was confirmed that: the concrete mold release agent of the invention exerts an excellent mold release effect between the concrete cured product in the mold frame and the mold frame, and the obtained concrete cured product has excellent surface appearance and can inhibit the generation of uneven color.

Industrial applicability

The auxiliary agent for a concrete mold release agent of the present invention can be used as an auxiliary agent to be mixed in a concrete mold release agent, and can exert a mold release property between a mold frame and concrete or the like in the production of concrete or the like. The concrete release agent of the present invention can be used as a release agent that exhibits a release property between a mold frame and concrete or the like in the production of concrete or the like.

Claims

1. An auxiliary agent for a concrete release agent, comprising:

a component (A) represented by the following general formula (1);

component (C) represented by the following general formula (2),

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;

the component (C) is contained in an amount of 5 to 50 parts by mass,

[ chemical formula 1]

In the general formula (1), R ¹ Is a residue obtained by removing a hydroxyl group from an aliphatic alcohol having 6 to 24 carbon atoms; r is R ² O is an oxyalkylene group having 2 to 4 carbon atoms, but when a plurality of the oxyalkylene groups are present, it is 1 or 2 or more kinds alone; r is R ³ Is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; n is an integer of 1 to 20,

[ chemical formula 2]

In the general formula (2), R ⁴ Is a residue obtained by removing a hydroxyl group from an aliphatic alcohol having 10 to 30 carbon atoms; r is R ⁵ O is an oxyalkylene group having 2 to 4 carbon atoms, but when a plurality of the oxyalkylene groups are present, it is 1 or 2 or more kinds alone; m is an integer of 26 to 100; however, when the ratio of the oxyalkylene groups having 2 to 4 carbon atoms is 100 mol% in total, - (R) in the general formula (2) ⁵ O) _m -an oxyalkylene group having 3 carbon atoms in a proportion of 70 to 100 mole%.

2. A concrete release agent comprising the auxiliary agent for a concrete release agent according to claim 1 and a base oil.

3. The concrete mold release agent according to claim 2, wherein,

when the content ratio of the auxiliary agent for a concrete mold release agent and the base oil is 100 parts by mass in total,

the auxiliary agent for the concrete release agent is contained in a proportion of 0.1 to 25 parts by mass,

the base oil is contained in a proportion of 75 to 99.9 parts by mass.

4. A concrete release agent comprising:

a base oil, the component (A) constituting the auxiliary agent for a concrete mold release agent according to claim 1, the component (B) constituting the auxiliary agent for a concrete mold release agent according to claim 1, and the component (C) constituting the auxiliary agent for a concrete mold release agent according to claim 1,

5. The concrete mold release agent according to claim 4, wherein,

when the content ratio of the base oil, the component (B), and the nonionic surfactant is 100 parts by mass in total,

The base oil is contained in a proportion of 70 to 98.95 parts by mass,

the component (B) is contained in an amount of 0.05 to 10 parts by mass,

the nonionic surfactant is contained in a proportion of 1 to 20 parts by mass.

6. A method for manufacturing concrete, comprising:

a coating step of coating the mold for concrete according to claim 2 or 3 on the inner surface of a mold for concrete,

7. A method for manufacturing concrete, comprising:

a coating step of coating the aqueous solution of the concrete release agent obtained by mixing the concrete release agent described in claim 4 or 5 with water on the inner surface of a concrete form;