JPH1119915A - Concrete releasant composition and its use method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly safe concrete releasant composition, which has performance excellent in the finishing properties of the surface of a concrete, a releasability, a workability and a storage stability, and its use. SOLUTION: This composition consists of 12-40 wt.% of mixed oils and fats in combination of oils and fats, which are solid or semi-solid at normal temperature and has an ascending melting point (measured by normal oils and fats analytical test method) of 20-60 deg.C and oils and fats, which are liquid at normal temperature or mineral oil as a base oil, 1.0-7 wt.% of nonionic surface active agent, the HLB of which is prepared to be 6.0-14.0 by mixing nonionic surface active agents having HLB values different from each other as an emulsifying agent, 0.3-6 wt.% of nonionic surface active agent as an auxiliary emulsifier and an oil film reinforcer, 0.2-6 wt.% of cyclic amine ethoxylate as water displacement type rust inhibitor and balance water so as to kae the whole as 100 wt.%. By applying a dispersion treatment with homogenizer to the composition, the composition is turned into finely divided particles having 0.1-10 μm in size.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a concrete release agent composition and a method for using the same, and more particularly, to the finish, release, rust prevention, form slime prevention, workability and storage stability of the concrete surface. The present invention relates to a concrete release agent composition having excellent properties and a method for using the same.

[0002]

2. Description of the Related Art Generally, the performance required as a concrete release agent is as follows. 1. Excellent release force. 2. The concrete surface finish is good. 3. Good storage stability. 4. No unpleasant odor. 5. High safety in use. 6. High economic efficiency. Workability is good.

[0003] In general, concrete release agents include an oily type provided by using animal and vegetable oils, mineral oils, and the like as a base oil, mixed with various additives such as fatty acids, surfactants, and waxes, and a base oil. And an emulsion type provided by mixing several kinds of additives and an emulsifier (surfactant) and diluting with water (or diluting with water in advance) at the time of use.

[0004] Advantages of the conventional oil-based type include excellent releasing force, little adhesion of scum to the mold, easy cleaning of the mold, and rust resistance of the mold. The product has many air bubbles, has oil burns, is a dangerous substance and has a poor working environment. Also, the advantages of the conventional emulsion type include that the appearance is white, the bubble is hardly formed in the product, the oil is not easily burned, and the working environment is good, but the disadvantages are that the releasing force is poor. Poor storage stability, large amount of scum, difficult to clean, mold rust easily.

[0005] As described above, the oil type and the emulsion type each have advantages and disadvantages.
Depending on the production environment, the oily type and the emulsion type may be used alone or in combination. However, recently, from the viewpoints of aesthetics, environmental problems, economy and the like of concrete products, the need for emulsion type (O / W type, W / O type) release agents has been increasing.

[0006]

In recent years, as concrete structures have become larger and more complicated, there has been a demand for improvements in technical capabilities including durability and aesthetics for concrete products. Very high quality is also required. However, in the case of conventional release agents, particularly emulsion-type release agents, the disadvantages of the emulsion-type release agents described above, that is, large amounts of scum adhered to the mold, making cleaning difficult, and poor release force In addition, there is a problem that the production efficiency is reduced and the quality of the concrete product is reduced because the mold does not have excellent performance in all of rust generation and storage stability.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and the performance required for a concrete release agent, that is, releasability, prevention of mold remaining, and finish of concrete surface (air bubbles) Prevention and color burn prevention), workability,
Another object of the present invention is to provide an emulsion-type concrete release agent composition having excellent performance in all storage stability and rich in safety, and a method for using the same.

[0008]

The inventor of the present invention has conducted intensive studies on the development of an emulsion-type concrete release agent which satisfies the above-mentioned performance. As a result, two types of nonionics having different HLB values as emulsifiers in a given oil or mineral oil. When a surfactant is used and a specific amount of a cationic surfactant is blended with the surfactant, it works effectively to strengthen the oil film and prevent residual sticking, and is compatible with a water displacement type rust inhibitor (cyclic amine ethoxylate). (E.g., silicon) is used to further improve the performance, and water is added to the mixture thus prepared to form a fine emulsion using a homogenizer, thereby providing excellent storage stability.
As soon as the emulsion was applied to the mold, it was found that the emulsion was destroyed and a strong oil-based coating film was formed, thereby completing the present invention.

That is, the present invention relates to (a) a base oil which is a solid or semi-solid at room temperature and has an ascending melting point (according to a standard fat and oil analysis test method) of 20 to 60 ° C. and a liquid at room temperature. Mixed fats or oils by combination
40% by weight, (b) Nonionic surfactants having different HLB values as emulsifiers and adjusting HLB to 6.0 to 14.0 by mixing 1.0 to 7% by weight of nonionic surfactants, (c) emulsification Cationic surfactant 0.3 ~ as auxiliary and oil film strengthening agent
6% by weight, (d) 0.2 to 6% by weight of cyclic amine ethoxylate as a water displacement type rust preventive agent, the remainder being 1
An O / W emulsion-type concrete release agent composition characterized in that the composition is set to 00% by weight, and the composition is subjected to a dispersion treatment with a homogenizer to form fine particles of 0.1 to 10 μm.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The emulsion-type concrete release agent composition of the present invention solves all the disadvantages without substantially impairing the advantages of the conventional emulsion-type concrete release agent. This will be described in detail.

Improvement of Release Force The base oil (oils) in the present invention is solid or semi-solid at room temperature, and has an ascending melting point (according to the standard fat and oil analysis test method) of 20 ° C. to 60 ° C. at room temperature. A mixed oil and fat is provided in combination with a liquid oil and fat, but by using a base oil as a mixed oil, the base oil has a better oil spreadability than that of only a liquid oil and fat at room temperature, and the releasing force is improved. . In addition, if only a solid or semi-solid fat at room temperature is applied with a release agent to a mold, the film thickness becomes a thick layer, which inhibits uniform wetting of the release agent and prevents oil burning and partial adhesion. Causes disadvantages. In the combination of the mixed fats and oils, it is preferable to mix at least 10% by weight of solid or semi-solid fats and oils at room temperature in consideration of mold releasability, oil burnt, emulsion stability and the like. If the amount of the mixed fat or oil is less than 12% by weight, the oil film of the release agent becomes too thin and the oil film is damaged, and if it is sufficient, the releasing force cannot be obtained. Similarly, if the addition amount exceeds 40% by weight, an excess of the release agent may remain, resulting in the generation of slime and the like, despite the fact that a sufficient release force is maintained. Defects such as oil burns and bubbles are generated in the surface finish due to the formation of a thick layer, and the economic effect is also deteriorated.

As a solid or semi-solid fat at normal temperature,
For example, palm oil, palm kernel oil, coconut oil, beef tallow, and hardened oils of various fats and oils can be mentioned. Examples of the fats and oils that are liquid at ordinary temperature include soybean oil, rapeseed oil, rice oil, sunflower oil, linseed oil, boiled oil thereof, and oil added with a small amount of water. One type or a mixture of two or more types of fats and oils and liquid fats and oils at room temperature is exemplified.

By using these mixed fats and oils, the emulsion is destabilized, a strong oil film is formed on the formwork, and the oil film is exhibited strong releasability without damaging the oil film during concrete casting or various vibrators. . Also, the use of a mineral oil, for example, kerosene, spindle oil, machine oil, or the like can maintain the releasing force.
The content of the mixed oil or mineral oil in the release agent composition is 1
2 to 40% by weight is suitable.

[0014] The surfactant used in the present invention is that most concrete products undergo steam curing during the manufacturing process, and since the concrete products have a high alkalinity, the ester bond portion has steam or strong alkali. Is considered to be easily susceptible to hydrolysis by oil, damage of oil film, generation of scum, etc. Those with excellent decomposability were selected.

Japanese Patent Publication No. 58-8602 discloses that addition of higher fatty acids and metallic soaps is effective as an oil film strengthening agent for emulsion-type concrete releasing agents. Fatty acids, metallic soaps and the like are contained in concrete. Reacts with the calcium salt of the mold to form and stick to the inner surface of the mold, so that it is difficult to clean.
In the present invention, an oil film can be effectively retained without blending such higher fatty acids and metal soaps. In order to strengthen the oil film, it is necessary to focus on the ionization tendency of each substance. Most concrete forms used in factories are iron (steel) forms. Since iron is negatively charged, the use of a cationic surfactant improves the oil adsorbing property and acts as an aid for strengthening the oil film. At that time, the emulsion is broken and a strong oil film is formed.
In addition, since the oil absorption to the mold is excellent, rust prevention performance can be added.

Preferred cationic surfactants have the general formula
It can be selected from primary to tertiary amine type cationic surfactants represented by (3) and quaternary ammonium type cationic surfactants represented by the following general formula (4). When the strength of the cationic surfactant is low, an organic acid and an inorganic acid are used in combination. The cationic surfactant includes an amphoteric surfactant, for example, a betaine type or an amino acid type.

[0017]

Embedded image Wherein R represents a C ₆ -C ₃₀ alkyl group or alkenyl group, R ₁ , R ₃ , and R ₄ represent a hydrogen atom, a C ₁ -C ₃₀ alkyl group or alkenyl group, or the following general formula X;

[0018]

Embedded image (Where, A is an alkylene group, m represents 1 to 50 of C ₁ -C ₄₎ is R ₂ is an ethylene group or a propylene group, n represents 0-6
Shows]

[0019]

Embedded image Wherein R is a C ₆ -C ₃₀ alkyl group or alkenyl group, and R ₁ , R ₂ , R ₄ , R ₅ , and R ₆ are a C ₁ -C ₃₀ alkyl group or alkenyl group or the following general formula Z Show,

[0020]

Embedded image (However, A represents a C ₁ -C ₄ alkylene group, m represents 1-50) [R ₃ is an ethylene group or a propylene group, and Y is
^{_{l -, CH 3 SO 4 -}} , ClO 4 - anions such, n represents 0-6
Shows]

Examples of the cationic surfactant represented by the general formula (3) include polyoxyethylene octadecylamine (EO 2 to 30 mol adduct), hydroxyethylene decylamine (EO 1 mol adduct), polyoxyethylene tallow amine (EO 2 to 30 mol adduct), polyoxyethylene tallow alkyl propylene diamine (EO 2 to 20 mol adduct), polyoxyethylene fatty acid amine ether (EO 2 to 20 mol adduct, cocoalkyldimeramine, oleylamine, dioleylamine, etc.) No.

Examples of the cationic surfactant represented by the general formula (4) include, for example, octadecyltrimethylammonium chloride, alkyl imidazolium chloride, tetradecylamine acetate, dimethyl palm alkyl betaine, methyl lauryl aminopropionate, and dimethyl palm alkyl. Betaine and the like.

Improving Storage Stability Storage stability is basically a major factor in the choice of surfactant, ie, emulsifier. However, the purpose is to select types, addition amounts, and combinations in which the performance as a release agent is not impaired and the performance is to be improved. That is, the present invention mixes nonionic surfactants having different HLB values (HLB = 1 to 6, HLB = 7 to 16) to adjust the HLB value to 6.0 to 14.0.
Adjusted to the minimum necessary for emulsification (1.0
-7% by weight), and in order to further improve the storage stability of the emulsion, a cationic surfactant is added in a specific amount (0.3 to
6% by weight).

The nonionic surfactant is represented by the following general formula:
Alkyl or alkenyl substituted phenol alkylene oxide adducts or higher alcohol alkylene oxide adducts represented by (1) and (2) are preferably used.

[0025]

Embedded image (Where R is a C ₆ -C ₃₀ alkyl or alkenyl group, and n is a number of 1-30)

[0026]

Embedded image (Where R is a C ₆ -C ₃₀ alkyl or alkenyl group, and n is a number of 1-30)

Examples of the nonionic surfactant represented by the general formula (1) include polyoxyethylene octyl phenyl ether (EO adduct of 2 to 30 mol), polyoxyethylene nonyl phenyl ether (EO adduct of 2 to 30 mol),
Polyoxyethylene decyl phenyl ether (EO2
30 mol adduct) and polyoxyethylene alkyl allyl ether (EO 2 to 30 mol adduct).
Examples of the nonionic surfactant represented by the general formula (2) include, for example, polyoxyethylene cetyl ether (EO2 to EO3).
0 mol adduct), polyoxyethylene stearyl ether (EO 2 to 30 mol adduct), polyoxyethylene dodecyl ether (EO 2 to 30 mol adduct), polyoxyethylene oleyl ether (EO 2 to 30 mol adduct), polyoxyethylene Ethylene lauryl ether (EO2
30 mol adduct), polyoxyethylene lanolin alcohol ether (EO 2 to 30 mol adduct), polyoxyalkylene alkyl ether (EO 2 to 30 mol adduct) and the like.

The larger the amount of the emulsifier added, the better the stability. On the other hand, the emulsifier reduces the water resistance of the oil film and deteriorates the releasability.
Affects the hydration reaction of concrete, generates scum,
Significantly, disadvantages such as the possibility of partial curing failure may occur.

The storage stability also depends on the size of the particles.
The finer the particle size, the better.
If it is less than 0.1, the Brownian motion tends to increase and coalesce. Therefore, the release agent is preferably about 0.1 to 10 μm, and more preferably about 0.2 to 5 μm. However, it is desirable that the particle size distribution has relatively little variation and the particle size is uniform. To homogenize the concrete release agent composition of the present invention using a homogenizer for the purpose of making the particles of the concrete release agent composition fine, and heating while controlling the temperature so that air is not entrained as much as possible. Is recommended. However, even if a homogenizer is used, if the selection and addition amount of the surfactant is insufficient and the emulsification conditions are not adjusted, an emulsion having a particle size of 10 to 30 μm and a wide and nonuniform particle size distribution may be obtained. However, this does not provide stability in a cycle test due to a change over time and a temperature change of 5 to 50 ° C., and has poor storage stability. In conventional emulsion-type release agents, the type that is diluted with water before use is the mainstream, and even if the emulsifier is used excessively, the particle size distribution is not uniform and the particle size is coarse because of normal stirring at room temperature. Storage stability after dilution is poor.

Inhibition of scum The generation of scum is caused by various factors such as a chemical reaction and a physical reaction. The concrete composition is hardened by the hydration reaction of the cement to generate calcium hydroxide and the like. The concrete release agent exists at the boundary between the formwork and concrete, but as mentioned above, additives that react with calcium etc. may cause scum, so the reaction must be suppressed as much as possible. No. The suppression of scum in the concrete release agent composition of the present invention can be demonstrated by using a cationic surfactant. However, considering the amount of the cationic surfactant added, the pH of the emulsion is 7 to 10,
Preferably, it is made 7.5 to 9 to make it weakly alkaline. When the pH of the emulsion exceeds 10, emulsification of the composition is inhibited, storage stability becomes extremely poor, and there is a possibility that hand-working or the like may occur, thus deteriorating the working environment. The film thickness of the concrete release agent is also responsible for the suppression of scum. The concrete release agent composition of the present invention is an emulsion obtained using a homogenizer, and the particle size is 0.2 to 10 μm.
m, preferably 0.2 to 5 μm, when applied to a mold, the single particle or the multilayer thickness of the single particle is 2 to 10 μm
m, preferably a 2-8 μm thick layer, so that the interfacial tension is low and no unnecessarily large release agent remains, and the generation of scum is suppressed while maintaining the release force, and oil burns are also prevented. . Fatty acids, etc., which are excellent in oil stiffeners, which are mostly used in conventional concrete release agents, are acids and cause a reaction. Reduce the amount as much as possible,
Or it is desirable not to use it at all for suppression of scum.

Improvement of rust prevention The concrete release agent composition of the present invention retains rust prevention by using a cationic surfactant. The addition of a cyclic amine ethoxylate rust inhibitor as a rust agent and, if necessary, a vaporizable rust inhibitor such as a fatty acid amine not only enhances the rust prevention property, but also makes the emulsion-type mold release agent more reusable after drying. The emulsification can be prevented, the releasing force can be maintained, and the stability of the oil film can be improved.

The cyclic amine ethoxylate has the following general formula
Although it can be represented by (5), for example, "Ramiproof C-2" (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like can be preferably used.

[0033]

Embedded image (However, X represents a cyclic amine residue and n represents a number of 1 to 4.) Examples of the cyclic amine residue include a cyclohexylamine residue.

Further, rust preventives, preservatives, thixotropic agents, thickeners, defoamers, etc., which are blended in conventional concrete release agents, can be used in the concrete release agent composition of the present invention. .

The emulsion concrete release agent composition prepared by emulsifying with a homogenizer while adding water and heating (about 40 to 60 ° C.) is diluted 1 to 5 times with water, preferably soft water, depending on the use. To use. This allows
The economical efficiency can be improved while maintaining the oil / fat film thickness for improving the surface finish of the concrete product.

As a method of applying the present composition to a concrete formwork, spraying, brushing, dripping, mopping, a roller method and the like are employed.

The emulsion-type concrete release agent composition obtained by the present invention has a feature that it has excellent storage stability and that the emulsion is destroyed immediately after it is applied to a mold, and a strong coating film is formed.

[0038]

The present invention will be described below in more detail with reference to examples and comparative examples. In Examples and Comparative Examples,
Means "parts by weight".

EXAMPLE 1 75% by weight of palm oil-palm oleic oil 25 as fat or oil
Solid oil consisting of 30% by weight (ascending melting point 33 ° C to 40 ° C) 14
Of polyoxyethylene nonylphenol ether (HLB) as an emulsifier in a mixed oil of 6 parts of liquid rapeseed oil and 6 parts of liquid rapeseed oil.
12) 2.0 parts [Nonion NS202 manufactured by NOF Corporation
S ”HLB 5.7; 25% by weight,“ Nonion N ”
S212 "HLB 14.1; 75% by weight], and polyoxyethylene alkylamine as a cationic surfactant.
5 parts (manufactured by NOF CORPORATION, "Nymeen T2-202") were added, and 0.5 parts of a fatty acid amine compound (manufactured by Kyrest Co., "Kirescoat ZB") as a rust preventive agent, and cyclic amine ethoxy as a water displacement rust preventive agent. Rate 0.5 part (Daiichi Kogyo Seiyaku Co., Ltd., “Ramiproof C-2”), 0.1 part of defoaming silicone as defoaming agent (Toshiba Silicone Co., Ltd., “TSA73
0 ") and stirred to dissolve. Then, 74.4 parts of water was added to adjust the temperature of the mixed solution to 27 ° C to 30 ° C. This composition was emulsified using a homomixer to obtain a predetermined emulsion-type composition. The performance was evaluated using a four-fold dilution of this with water.
The performance evaluation of this composition was performed with respect to mold release properties, the presence or absence of mold residue, the presence or absence of bubbles and coloring in the finish of the concrete surface, the rust prevention, and the storage stability of the release agent. The test results are shown in [Table 2- (1)] and [Table 3-
(1)].

Example 2 In Example 1, 2.0 parts of polyoxyethylene alkylamine (manufactured by NOF CORPORATION,
The base oil and other additives were the same as in Example 1 except that "Nymeen DT-203") and 0.5 parts of tallow alkylmethylammonium chloride ("Nissan Cation ABT2-500" manufactured by NOF Corporation) were used. An emulsion-type composition was obtained under the same production conditions with the compounding amounts shown in [Table 1- (1)]. An evaluation test similar to that of Example 1 was performed using a product obtained by diluting the product four times with water. The results are shown in [Table 2- (1)] and [Table 3- (1)].

Example 3 In Example 1, polyoxyethylene lauryl ether [manufactured by NOF CORPORATION, "Nonion K-20" as an emulsifier was used.
1 "(HLB 3.6)] and 0.8 parts of polyoxyethylene oleyl ether [Nonion E-21 manufactured by NOF Corporation
5 "(HLB 14.2)] and 2.2 parts of a mixture of two types (HLB 12.1), and the same base oil and other additives as in Example 1 were used. 1- (1)], an emulsion-type composition was obtained under the same production conditions with the amounts shown. An evaluation test similar to that of Example 1 was performed using a product obtained by diluting this water twice. The results are shown in [Table 2- (1)] and [Table 3- (1)].

Example 4 Other additives were the same as in Example 1 except that 15 parts of a mixed oil consisting of 70% by weight of machine oil and 30% by weight of spindle oil was used as a mineral oil in place of the mixed oil and fat. An emulsion-type composition was obtained under the same production conditions with the same amounts as shown in [Table 1- (1)] using the same composition as described above. An evaluation test similar to that of Example 1 was performed using a product obtained by diluting the product four times with water. The results are shown in [Table 2- (1)] and [Table 3
-(1)].

Example 5 25 parts of a mixed oil composed of 70% by weight of a machine oil as a mineral oil and 30% by weight of a spindle oil, and 3.0 parts of a polyoxyethylene alkylamine as a cationic surfactant [manufactured by NOF CORPORATION; L-201 "; 75% by weight," Nymeen F-215 "; 75% by weight], and polyoxyethylene lauryl ether (HL
B 7.4) 4.0 parts [Nonion K-20, manufactured by NOF Corporation
1 "(HLB 3.6); 70% by weight," Nonion K-220 "(HLB 16.2); 30% by weight, manufactured by the same company], and the other additives were the same as those in Example 1. To obtain an emulsion-type composition under the same production conditions with the compounding amounts shown in [Table 1- (1)]. An evaluation test similar to that of Example 1 was performed using a product obtained by diluting the product four times with water. The results are shown in [Table 2- (1)] and [Table 3- (1)].

Example 6 In Example 1, a solid oil consisting of 65% by weight of coconut oil-35% by weight of lard as a base oil (increased melting point: 29 ° C.)
-36 ° C) Except that a mixed oil of 10 parts and 15 parts of liquid castor oil was used, the other additives were the same as in Example 2 and the blending amounts shown in Table 1- (1) were used. Under the same production conditions to obtain an emulsion-type composition. An evaluation test similar to that of Example 1 was performed using the product diluted 4 times with water. The results are shown in [Table 2- (1)] and [Table 3- (1)].

Example 7 In Example 6, except that 2.0 parts of polyoxyethylene alkylamine ether (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., “Carazole WLM56”) was used as the cationic surfactant, the other additives were used. [Table 1]
-(1)] An emulsion composition was obtained under the same production conditions with the compounding amount shown in [1]. An evaluation test similar to that of Example 1 was performed using a product obtained by diluting this water twice. The results are shown in [Table 2- (1)] and [Table 3- (1)].

Example 8 In Example 1, 3.2 parts of polyoxyethylene alkylamine (manufactured by Nippon Emulsifier Co., Ltd.) was used as a cationic surfactant.
Other additives were the same as in Example 1 except that "Newco 145") and 1.3 parts of dimethyl cocoalkyl betaine ("Nissan Anone BF" manufactured by NOF Corporation) were used [Table 1]. -(1)] An emulsion composition was obtained under the same production conditions with the compounding amount shown in [1]. An evaluation test similar to that of Example 1 was performed using a product obtained by diluting this water twice. The results are shown in [Table 2- (1)] and [Table 3- (1)].

Example 9 In Example 1, the base oil and other additives were the same as in Example 1 except that 1.0 part of silicone oil ("TSF4440" manufactured by Toshiba Silicone Co., Ltd.) was used as a compatibilizer. An emulsion-type composition was obtained under the same production conditions with the compounding amounts shown in [Table 1- (1)]. An evaluation test similar to that of Example 1 was performed using a product obtained by diluting the product four times with water. The results are shown in [Table 2- (1)] and [Table 3-
(1)].

Comparative Example 1 In Example 1, except that no cationic surfactant was added, the same base oil and the same additives were used and the blending amounts shown in [Table 1- (2)] were used under the same production conditions. An emulsion composition was obtained. An evaluation test similar to that of Example 1 was performed using a product obtained by diluting the product four times with water. The results are shown in [Table 2- (2)] and [Table 3- (2)].

Comparative Example 2 In Example 1, the same base oil and additive were used except that no cyclic amine ethoxylate as a water displacement type rust inhibitor was added at all, and the blending amount shown in [Table 1- (2)] was used. With the same production conditions, an emulsion composition was obtained.
An evaluation test similar to that of Example 1 was performed using a product obtained by diluting the product four times with water. The results are shown in [Table 2- (2)],
It is shown in [Table 3- (2)].

Comparative Example 3 An emulsion was prepared in the same manner as in Example 5 except that no cationic surfactant was added, and the same base oil and additives were used and the blending amounts shown in [Table 1- (2)] were used. A mold composition was obtained. An evaluation test similar to that of Example 1 was performed using a product obtained by diluting the product four times with water.
The results are shown in [Table 2- (2)] and [Table 3- (2)].

COMPARATIVE EXAMPLE 4 An emulsion was prepared in the same manner as in Example 6 except that no cationic surfactant was added, using the same base oil and additives, and at the blending amounts shown in Table 1- (2). A mold composition was obtained. An evaluation test similar to that of Example 1 was performed using a product obtained by diluting the product four times with water.
The results are shown in [Table 2- (2)] and [Table 3- (2)].

Comparative Example 5 In Example 7, the same base oil and additive were used except that no cyclic amine ethoxylate as a water displacement type rust inhibitor was added at all, and the compounding amount shown in [Table 1- (2)] was used. With the same production conditions, an emulsion composition was obtained.
An evaluation test similar to that of Example 1 was performed using a product obtained by diluting this water twice. The results are shown in [Table 2- (2)],
It is shown in [Table 3- (2)].

Comparative Example 6 In Example 1, 0.4 part of a solid oil composed of 75% by weight of palm oil-25% by weight of palm olein oil (rising temperature: 33 ° C. to 40 ° C.) as a base oil and liquid rapeseed oil
Except for using a mixed oil with 6 parts, the other additives were the same as in Example 1 to obtain an emulsion-type composition under the same production conditions with the compounding amounts shown in [Table 1- (2)]. Was.
An evaluation test similar to that of Example 1 was performed using a product obtained by diluting this water twice. The results are shown in [Table 2- (2)],
It is shown in [Table 3- (2)].

Comparative Example 7 In Example 1, 8.75 parts of a solid oil composed of 75% by weight of palm oil-25% by weight of palm olein oil (ascending melting point: 33 ° C. to 40 ° C.) as a base oil and liquid rapeseed oil 4
Emulsion-type composition was prepared under the same production conditions using the same additives as in Example 1 except that a mixed oil with 1.25 parts was used and having the compounding amount shown in [Table 1- (2)]. I got An evaluation test similar to that of Example 1 was performed using a product obtained by diluting the product four times with water. The results are shown in [Table 2-
(2)] and [Table 3- (2)].

Comparative Example 8 In Example 1, 9.0 parts of polyoxyethylene alkylamine (manufactured by NOF CORPORATION,
Emulsion-type composition under the same production conditions using the same base oil and other additives as in Example 1 except that "Nymeen T2-202") was used and with the blending amounts shown in [Table 1- (2)]. I got something. An evaluation test similar to that of Example 1 was performed using a product obtained by diluting the product four times with water. The results are shown in [Table 2- (2)] and [Table 3- (2)].

Comparative Example 9 In Example 1, 9.0 parts of a polyoxyethylene nonylphenol ether (HLB12) ("Nonion NS202S"HLB5.7; manufactured by NOF Corporation) was used as an emulsifier.
25% by weight of the company “Nonion NS212” HLB 1
4.1; 75% by weight of a mixture) and the same base oil and other additives as in Example 1 with the blending amounts shown in [Table 1- (2)] under the same production conditions. An emulsion composition was obtained. An evaluation test similar to that of Example 1 was performed using a product obtained by diluting the product four times with water. The results are shown in [Table 2- (2)] and [Table 3- (2)].

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

[Table 2- (1), (2)], [Table 3- (1),
(2)] As is clear from the test results of Example No. 1-9
Are mold release properties, mold frame remaining stickiness, surface finish properties,
It has excellent rust prevention and storage stability, and gives very good results regardless of the size of the concrete product. In particular, with regard to the mold remaining residue that could not be achieved with the conventional emulsion mold release agent, no residue remained in the mold, significantly improving workability and no concrete residue adhesion on the concrete product side. It was found that the concrete product was very beautiful.

On the other hand, in Comparative Example No. 1, No. 3, N
o. Excluding the cationic surfactant used in the product of the present invention as in 4, the mold releasability is poor, a large amount of residual mold remains, and there are many air bubbles in the concrete surface finish. Comparative Example No. 2, No. Excluding the water-substituted rust preventive cyclic amine ethoxylate used in the product of the present invention as shown in 5, the release property and the rust preventive property are deteriorated. Comparative Example No. When the blended amount of the mixed fat or oil is less than 12% by weight as in 6, the release property and the storage stability are deteriorated. Comparative Example No. If the blending amount of the mixed fat or oil exceeds 40% by weight as shown in 7, the releasability, the residual mold residue, the finish on the concrete surface, and the storage stability deteriorate. Comparative Example No. When the amount of the cationic surfactant exceeds 6% by weight, as in 8, the remaining mold and the finish of the concrete surface deteriorate. Comparative Example No. When the amount of the nonionic surfactant exceeds 7% by weight as in No. 9, even if the cationic surfactant is used, it is understood that the releasability, the mold remaining residue and the concrete surface finish are poor.

Table 2 shows the test results of the above release agents.
(1)] and [Table 2- (2)] are 1200 × 1400 × 2
A predetermined mold release agent was applied to a steel mold having a common groove of 000, concrete was driven into the mold, the mold was vibrated at 3000 Vpm for 1 minute, and the mold was removed after steam curing at 60 ° C. for 5 hours. . [Table 3- (1)] and [Table 3- (2)]
A predetermined mold release agent is applied to a steel mold having a U-shaped groove of 0x700x2000, concrete is poured in, and the concrete is vibrated for 2 minutes with a table vibrator, and further vibrated for 1 minute and 30 seconds with a bar vibrator. Demolding was performed after steam curing at 6 ° C. for 6 hours. The criteria for each item are described below.

<Judgment Criteria> (Judgment) (Criterion) Releasability ×: Unless the formwork is hit, it does not come off and is extremely difficult to remove. △: Partial sticking and difficult to remove ○: There is no sticking, but it is difficult to remove the mold a little ◎… Easy to remove the mold Remaining slag × …… Thickly adheres to the entire surface of the mold △:… Thinly adheres to the entire surface of the mold ○ …… Partially adheres ◎… … No adhesion Air bubbles × …… Large bubbles on the entire surface △ …… Small bubbles on the entire surface ○ …… Partially small bubbles ◎ …… No bubbles多 い 多 い 多 い… 一部 一部 一部 一部 一部 一部 一部 一部 多 い 一部 一部 多 い 多 い 多 い 多 い 多 い 一部 週 間 週 間 週 間 週 間 週 間 週 間 週 間There is rust ◎… No rust even if used for more than one month Storage stability × ...... 1 day left to those to separate △ ...... 1 month stand to those to separate ○ ...... 1 month stand to those not separate ◎ ...... 3 months stand to those that do not separate

[0064]

As described above, the emulsion-type concrete release agent composition of the present invention provides the performance required for the production of concrete products, that is, the releasability, finish of concrete surface, workability, and storage. Demonstrates excellent performance for all stability. Therefore, if these concrete release agent compositions are used, high quality concrete products can be maintained, and production efficiency does not decrease.

Claims (5)

[Claims] (1) A mixed fat or oil as a base oil which is solid or semi-solid at normal temperature and has an ascending melting point (according to a standard fat and oil analysis test method) of 20 to 60 ° C. and a liquid fat at normal temperature. Or 12-40% by weight of mineral oil,
(B) Nonionic surfactants having different HLB values mixed with each other as emulsifiers to adjust HLB to 6.0 to 14.0; 1.0 to 7% by weight of nonionic surfactants; (c) emulsifying aid and oil film 0.3 to 6% by weight of a cationic surfactant as a reinforcing agent,
(d) 0.2 to 6% by weight of cyclic amine ethoxylate as a water-replacement type rust inhibitor, the remainder being made up to 100% by weight with water, and the composition being subjected to a dispersion treatment with a homogenizer to obtain 0.1 to 10% by weight. O / W emulsion-type concrete release agent composition characterized by being finely divided to 10 μm 2. The nonionic surfactant has the following general formula:
The O according to claim 1, which is an alkyl or alkenyl substituted phenol alkylene oxide adduct or a higher alcohol alkylene oxide adduct represented by (1) or (2).
/ W emulsion-type concrete release agent composition (Where R represents a C ₆ -C ₃₀ alkyl group or alkenyl group, and n represents 1-30). (Where R is a C ₆ -C ₃₀ alkyl or alkenyl group, and n is a number of 1-30) 3. The method according to claim 1, wherein the cationic surfactant has the following general formula:
2. The compound according to claim 1, which is a compound represented by (3) or (4).
/ W emulsion-type concrete release agent composition Wherein R is a C _{6 to} C ₃₀ alkyl or alkenyl group, R ₁ , R ₃ and R ₄ are a hydrogen atom, a C _{1 to} C ₃₀ alkyl or alkenyl group or the following general formula X; Formula 4 (However, A represents a C ₁ -C ₄ alkylene group, m represents 1-50), R ₂ represents an ethylene group or a propylene group, and n represents 0-6. Wherein R is a C ₆ -C ₃₀ alkyl or alkenyl group, R ₁ , R ₂ , R ₄ , R ₅ and R ₆ are a hydrogen atom, a C ₁ -C ₄ alkyl or alkenyl group, or Which represents formula Z, (However, A represents a C ₁ -C ₄ alkylene group, m represents 1-50) R ₃ represents an ethylene group or a propylene group, and Y represents Cl ⁻ ,
Anions such as CH ₃ SO ₄ ⁻ and ClO ₄ ⁻ , and n represents 0 to 6] 4. The O / W emulsion-type concrete release agent composition according to claim 1, wherein the water displacement type rust preventive is a cyclic amine ethoxylate represented by the following general formula (5). (Where X is a cyclic amine residue and n is a number from 1 to 4) 5. The concrete release agent according to claim 1, wherein the O / W emulsion type concrete release agent composition is diluted with water in an amount of 1 to 5 times the amount of water and applied to a mold. How to use the composition