Aesthetic additive for hydraulic compositions, hydraulic compositions, concrete, and methods for producing concrete.

Abstract

This invention improves the aesthetic appearance of a hydraulic composition after curing, while suppressing its influence on the amount of air it contains. [Solution] The aesthetic additive for hydraulic compositions contains the following ethyleneamine derivative (A). Ethyleneamine derivative (A): It includes at least one adduct obtained by directly adding propylene oxide to ethyleneamine, which is at least one of ethylenediamine and diethylenetriamine, and a block adduct obtained by further adding ethylene oxide to the adduct, wherein the total average number of moles of propylene oxide and ethylene oxide added per mole of ethyleneamine is 10 moles or more and 200 moles or less, and the ratio of the average number of moles of propylene oxide added to the total average number of moles of propylene oxide and ethylene oxide added is 40% or more and 100% or less.

Description

Technical Field

[0001] The present invention relates to an aesthetic improvement additive for a hydraulic composition, a hydraulic composition ,Ko for concrete and Biko a method for producing concrete.

Background Art

[0002] A hydraulic composition is a composition containing a hydraulic substance such as cement. For example, concrete is a hydraulic composition obtained by mixing cement, aggregate, and water, and the hardened concrete is widely used as building materials and the like.

[0003] Among concretes, for the purpose of assembly and installation at a construction site or the like, concrete products and concrete members manufactured using a ready-made formwork at a factory or the like are called precast concrete. In recent years, the use of precast concrete has been promoted from the viewpoints of improving work efficiency and reducing the number of workers engaged in the work.

[0004] In precast concrete, defects such as air bubble marks on the surface of the product after demolding from the formwork and depressions due to insufficient filling of the hydraulic composition may occur. If defects occur on the surface of the precast concrete due to such defects, the aesthetics deteriorate. Therefore, the surface aesthetics of precast concrete is an important factor determining the value of the product. Currently, air bubble marks, depressions due to insufficient filling, etc. are generally repaired manually, and there are problems in terms of production efficiency and manufacturing cost.

[0005] In order to improve the aesthetics of the hardened hydraulic composition, for example, techniques regarding surface aesthetics improvers for cement molded products have been proposed. For example, Japanese Patent Laid-Open No. 11-199290 (Patent Document 1) provides a surface aesthetics improver for a cement molded product containing a polyalkylene glycol derivative composed of a polypropylene oxide adduct of polyethylene glycol and / or a polypropylene oxide adduct of an ethylene diamine polyethylene oxide adduct. The surface aesthetics improver is further said to contain a water reducing agent. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 11-199290 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, the surface aesthetics improving agent described in Patent Document 1 is not sufficiently effective in improving the surface aesthetics of cement molded products, and there is still room for improvement. Furthermore, hydraulic compositions need to be adjusted to have an air content within a predetermined range in order to improve durability and workability after hardening, but since the surface aesthetics improving agent described in Patent Document 1 reduces the amount of air in the concrete (i.e., defoaming), thereby reducing the amount of air that appears on the surface, using it in a hydraulic composition may make it difficult to adjust the air content of the concrete. Thus, the surface aesthetics improving agent described in Patent Document 1 also has problems in practical use.

[0008] Therefore, an aesthetic enhancement additive that can improve the surface aesthetics of a hardened hydraulic composition by suppressing the influence on the amount of air in the hydraulic composition, and in particular by reducing the generation of surface bubbles, and a hydraulic composition using the same. ,Ko Concrete Oyo Biko A method for manufacturing concrete is required. [Means for solving the problem]

[0009] The aesthetic additive for hydraulic compositions according to the present invention contains the following ethyleneamine derivative (A): It is used in hydraulic compositions for forming precast concrete or cast-in-place concrete that is formed using formwork. It is characterized by the following: Ethyleneamine derivative (A): Includes at least one adduct obtained by directly adding propylene oxide to ethyleneamine, which is at least one of ethylenediamine and diethylenetriamine, and at least one block adduct obtained by further adding ethylene oxide to the adduct, wherein the sum of the average number of moles of propylene oxide and ethylene oxide added per mole of ethyleneamine is 60 More than a mole 100 The number of moles is less than or equal to 100%, and the ratio of the average number of moles of propylene oxide added to the total average number of moles of propylene oxide and ethylene oxide added is 40% or more and 100% or less.

[0010] The hydraulic composition according to the present invention Formed using a mold Precast concrete or cast-in-place concrete A hydraulic composition for use in molding, comprising hydraulic powder, aggregate, water, and an aesthetic additive for the hydraulic composition, characterized in that the content of the aesthetic additive for the hydraulic composition is greater than 0 parts by mass and 2.0 parts by mass or less per 100 parts by mass of the hydraulic powder.

[0011] The present invention relates to Ruko Concrete is a hardened body of the above hydraulic composition. And, whether precast concrete or cast-in-place concrete It has a certain characteristic.

[0012] The present invention relates to Ruko The concrete manufacturing method comprises a hydraulic composition preparation step of preparing a hydraulic composition by mixing hydraulic powder, aggregate and water, and a filling step of filling a formwork with the hydraulic composition. Or it is cast-in-place concrete, concrete A method for manufacturing the hydraulic composition, wherein in the step of preparing the hydraulic composition, Contains the following ethyleneamine derivative (A) The present invention is characterized by mixing an aesthetic additive for hydraulic compositions in a ratio of more than 0 parts by mass and 2.0 parts by mass or less per 100 parts by mass of the hydraulic powder. Ethyleneamine derivative (A): The present invention comprises at least one adduct obtained by directly adding propylene oxide to ethyleneamine, which is at least one of ethylenediamine and diethylenetriamine, and at least one block adduct obtained by further adding ethylene oxide to the adduct, The total average number of moles of propylene oxide and ethylene oxide added per mole of ethyleneamine is 10 moles or more and 200 moles or less, and the ratio of the average number of moles of propylene oxide added to the total average number of moles of propylene oxide and ethylene oxide added is 40% or more and 100% or less.

[0013] As a result of intensive studies on the above problems, the present inventors have found that by adding an appearance-improving additive containing a specific ethyleneamine derivative (A) to the hydraulic composition, it is possible to improve the surface appearance of the hardened body while suppressing the influence on the amount of air in the hydraulic composition, and have thus completed the present invention. According to the above configuration, since the occupancy rate of bubbles on the surface of the hardened body of the hydraulic composition can be reduced to improve the surface appearance, the repair process for the hardened body after production can be reduced, and the production efficiency can be improved. The appearance-improving additive of the present invention is excellent in usability because it hardly affects the amount of air in the hydraulic composition even when added.

[0014] Hereinafter, preferred embodiments of the present invention will be described. However, the scope of the present invention is not limited by the preferred embodiment examples described below.

[0015] As one aspect, the appearance-improving additive for a hydraulic composition according to the present invention preferably contains ethylenediamine as the ethyleneamine. <0OO0086>

[0016] According to this configuration, the surface appearance is more likely to be further improved.

[0017] As one aspect, the appearance-improving additive for a hydraulic composition according to the present invention preferably has a ratio of the average number of moles of propylene oxide added to the total average number of moles of propylene oxide and ethylene oxide added of 60% or more and 95% or less.

[0018] According to this configuration, the surface appearance is more likely to be further excellent, and it hardly affects the amount of air in the hydraulic composition.

[0019] Further features and advantages of the present invention will become more apparent from the following illustrative and non-limiting description of embodiments.

Embodiments for Carrying Out the Invention

[0020] Embodiments of the appearance-improving additive for a hydraulic composition, the hydraulic composition, precast concrete, and a method for producing precast concrete according to the present invention will be described.

[0021] [Composition of aesthetic additives for hydraulic compositions] The aesthetic additive for hydraulic compositions according to this embodiment (hereinafter also simply referred to as the aesthetic additive) contains an ethyleneamine derivative (A).

[0022] The ethyleneamine derivative (A) according to this embodiment is an adduct obtained by directly adding propylene oxide to ethyleneamine, which is at least one of ethylenediamine and diethylenetriamine, or a block adduct obtained by further adding ethylene oxide to an adduct obtained by directly adding propylene oxide to ethyleneamine, which is at least one of ethylenediamine and diethylenetriamine.

[0023] In this embodiment, the ethyleneamine derivative (A) is characterized in that the total average number of moles of propylene oxide and ethylene oxide added per mole of ethyleneamine is 10 moles or more and 200 moles or less. Furthermore, in the ethyleneamine derivative (A) according to this embodiment, the ratio of the average number of moles of propylene oxide added to the total average number of moles of propylene oxide and ethylene oxide added is 40% or more and 100% or less.

[0024] The ethyleneamine in ethyleneamine derivative (A) forms the central ethyleneamine skeleton in ethyleneamine derivative (A). The ethyleneamine is not limited as long as it is at least one of ethylenediamine and diethylenetriamine. The ethyleneamine may be ethylenediamine alone, diethylenetriamine alone, or both ethylenediamine and diethylenetriamine. Among these, it is preferable that the ethyleneamine contains ethylenediamine. With this configuration, surface aesthetics are more easily improved.

[0025] The ethyleneamine derivative (A) according to this embodiment can be produced by adding propylene oxide (PO) to a starting material having an ethyleneamine skeleton in the presence of a catalyst. Alternatively, it can be produced by further adding ethylene oxide (EO) to the adduct. The starting material may be ethyleneamine itself (ethylenediamine, diethylenetriamine) or an ethyleneamine substituted product in which some or all of the hydrogen atoms are substituted. Non-limiting examples of ethyleneamine substituted products include N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine. This compound is a compound in which a 2-hydroxypropyl group is bonded to each of the four bonds of the nitrogen atom of ethylenediamine, and in the produced adduct, the 2-hydroxypropyl group has the same structure as the propyleneoxy group to which propylene oxide (PO) is added. The starting material having an ethyleneamine skeleton is preferably selected from the group consisting of ethyleneamine itself and ethyleneamine substituted products in which one or more hydrogen atoms bonded to the nitrogen atom are substituted with a 2-hydroxypropyl group.

[0026] The ethyleneamine derivative (A) according to this embodiment includes one of the following adducts A1 and A2, which contain a structural unit in which propylene oxide (PO) is directly added to ethyleneamine. (A1) Adduct obtained by directly adding propylene oxide (PO) to ethyleneamine. (A2) A block adduct obtained by directly adding propylene oxide (PO) to ethyleneamine, to which ethylene oxide (EO) is further added.

[0027] When ethyleneamine is ethylenediamine, the ethyleneamine derivative (A1) has the chemical structure of formula (1) shown below. [ka] In equation (1), x1 represents the average number of moles of propylene oxide (PO) added by block addition to one of the four bonds of ethylenediamine.

[0028] Ethyleneamine derivative (A2) is a block adduct obtained by addition polymerization of ethyleneamine with propylene oxide (PO) and ethylene oxide (EO), in the order of propylene oxide (PO) followed by ethylene oxide (EO). Ethyleneamine derivative (A2) can also be described as a compound in which polyethylene oxide adducts are formed at each end of the polypropylene oxide adduct of ethyleneamine.

[0029] When ethyleneamine is ethylenediamine, the ethyleneamine derivative (A2) has the chemical structure of formula (2) shown below. [ka] In equation (2), x² represents the average number of moles of propylene oxide (PO) added by block addition to one of the four bonds of ethylenediamine, and y represents the average number of moles of ethylene oxide (EO) added by block addition to the terminal of each block-added propylene oxide.

[0030] As shown in formulas (1) and (2), the ethyleneamine derivative (A) according to this embodiment is a PO adduct of ethyleneamine or a PO-EO adduct of ethyleneamine, and therefore exhibits different properties from that of an EO-PO adduct of ethyleneamine. Compared to an EO-PO adduct of ethyleneamine, the ethyleneamine derivative (A), which is a PO adduct of ethyleneamine or a PO-EO adduct of ethyleneamine, can reduce surface bubbles in the cured product, reduce the process of repairing the cured product after manufacturing, and improve production efficiency. Furthermore, it has little effect on the air content of the hydraulic composition, and hydraulic compositions can be easily manufactured simply by adding it without changing equipment or other factors.

[0031] The aesthetic enhancement additive is used in hydraulic compositions applied to areas where appearance is important, and the formulation of the hydraulic composition is determined based on the formulation of hydraulic compositions applied to areas where appearance is not a concern. In this case, since the quality standard for the amount of air in the hydraulic composition does not usually change regardless of the presence or absence of the aesthetic enhancement additive, adjustments are made to change the amount of air-entraining agents (AE agents) and defoaming agents to counteract the effect of the aesthetic enhancement additive on the amount of air. The aesthetic enhancement additive according to this embodiment has little effect on the amount of air in the hydraulic composition, making it easy to adjust the amount of air, and allowing for the suppression of the amount of air-entraining agents (AE agents) and defoaming agents.

[0032] The ethyleneamine derivative (A) according to the present invention has a total average number of moles of propylene oxide (PO) and ethylene oxide (EO) added per mole of ethyleneamine of 10 moles or more and 200 moles or less. When the total average number of moles of propylene oxide (PO) and ethylene oxide (EO) added per mole of ethyleneamine is within the above range, the surface aesthetics tend to be excellent. Preferably, the total average number of moles of propylene oxide (PO) and ethylene oxide (EO) added per mole of ethyleneamine is 40 moles or more and 150 moles or less, and more preferably 60 moles or more and 100 moles or less. In the ethyleneamine derivative (A1) of the above formula (1) in which ethyleneamine is replaced with ethylenediamine, x1 is one-quarter of the average number of moles of propylene oxide (PO) added per mole of ethyleneamine. Furthermore, in the ethyleneamine derivative (A2) of formula (2) above, where ethyleneamine is replaced with ethylenediamine, (x² + y) is one-quarter of the total average number of moles of propylene oxide (PO) and ethylene oxide (EO) added per mole of ethyleneamine.

[0033] The ethyleneamine derivative (A) according to the present invention has a ratio of the average number of moles of propylene oxide (PO) added to the total average number of moles of propylene oxide (PO) and ethylene oxide (EO) added of 40% or more and 100% or less. When the ratio of the average number of moles of propylene oxide (PO) added to the total average number of moles of propylene oxide (PO) and ethylene oxide (EO) added is within the above range, the surface aesthetics are easily improved and the amount of air in the hydraulic composition is less likely to be affected. The ratio of the average number of moles of propylene oxide (PO) added to the total of propylene oxide (PO) and ethylene oxide (EO) is preferably 60% or more and 95% or less, and more preferably 65% ​​or more and 90% or less.

[0034] [Method for producing an aesthetic additive for hydraulic compositions] Among the ethyleneamine derivatives (A) contained in the aesthetic additive according to this embodiment, the adduct (A1) in which propylene oxide (PO) is directly added to ethyleneamine can be produced, for example, by using an ethyleneamine substituted product (for example, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine) as a starting material, charging it in a pressure vessel with a catalyst such as potassium hydroxide, tert-butoxypotassium, and sodium methoxide, raising the temperature of the reaction system, performing dehydration under reduced pressure, and then gradually adding propylene oxide (PO) while maintaining the temperature of the reaction system to carry out addition polymerization. Furthermore, the ethyleneamine derivative (A2) can be produced by further gradually adding ethylene oxide (EO) to the ethyleneamine derivative (A1) obtained by the above method to carry out addition polymerization. It is preferable to neutralize the obtained adducts of A1 and A2 and purify them by filtration to obtain purified products. The ethyleneamine derivative obtained as a purified product may be used as is (non-volatile content) as an aesthetic additive for hydraulic compositions, or it may be used after being diluted with mixing water or the like.

[0035] The aesthetic enhancement additive according to this embodiment may be in a product form that includes other additives in addition to the usage methods described above. Examples of other additives include, but are not limited to, blackening inhibitors, strength enhancers, setting retarders, air entrainers (also called AE agents), defoamers, shrinkage reducers, thickeners, preservatives, and rust inhibitors.

[0036] [Hydraulic composition] The hydraulic composition according to this embodiment is a hydraulic composition used for molding precast concrete, and contains hydraulic powder (cement), aggregate (fine aggregate, coarse aggregate), water, and an aesthetic additive for the hydraulic composition.

[0037] The hydraulic powder (cement) contained in the hydraulic composition according to this embodiment is not particularly limited. Non-limiting examples of cement include various types of Portland cement such as ordinary Portland cement, moderate-heat Portland cement, low-heat Portland cement, rapid-hardening Portland cement, and sulfate-resistant Portland cement, as well as blast furnace cement, fly ash cement, and silica fume cement.

[0038] The hydraulic composition according to this embodiment may further contain admixtures in addition to the hydraulic powder (cement) described above. Non-limiting examples of admixtures include fly ash, blast furnace slag powder, limestone powder, stone powder, silica fume, expansive agents, anhydrous gypsum, hemihydrate gypsum, and dihydrate gypsum.

[0039] The water contained in the hydraulic composition according to this embodiment is not particularly limited. The water may be, but is not limited to, tap water, industrial water, deionized water, distilled water, etc.

[0040] The aggregate included in the hydraulic composition according to this embodiment is not particularly limited. Non-limiting examples of fine aggregate include river sand, mountain sand, land sand, sea sand, silica sand, crushed sand, and various slag fine aggregates. The fine aggregate may also contain fine-grained components such as clay. Non-limiting examples of coarse aggregate include river gravel, mountain gravel, land gravel, crushed stone, various slag coarse aggregates, and lightweight aggregates.

[0041] The hydraulic composition according to this embodiment may contain a dispersant. The dispersant may be one of the dispersants known for use in hydraulic compositions. Non-limiting examples of such dispersants include polycarboxylic acid copolymers, phosphate ester copolymers, naphthalene condensates, melamine condensates, phenol condensates, and lignin sulfonates. Commercially available dispersants may also be used. Examples of commercially available dispersants include water-reducing agents, AE water-reducing agents, high-performance water-reducing agents, and high-performance AE water-reducing agents.

[0042] The hydraulic composition according to this embodiment may contain other components besides those listed above, as long as the effect is not impaired. Examples of such other components include, but are not limited to, curing accelerators, setting retarders, air entrainers (also called AE agents), defoamers, shrinkage reducers, thickeners, preservatives, and rust inhibitors. These components may also be included in additives for hydraulic compositions. That is, any of the components exemplified above may be added as components of additives for hydraulic compositions, or they may be added as components separate from additives for hydraulic compositions during the manufacturing stage of the hydraulic composition.

[0043] The hydraulic composition according to this embodiment contains the above-mentioned aesthetic additive for hydraulic compositions in an amount exceeding 0 parts by mass and up to 2.0 parts by mass per 100 parts by mass of hydraulic powder. More preferably, the above-mentioned aesthetic additive for hydraulic compositions may contain 0.01 parts by mass or more and up to 2.0 parts by mass per 100 parts by mass of hydraulic powder. The content of the aesthetic additive for hydraulic compositions used when calculating the content ratio of the aesthetic additive for hydraulic compositions to hydraulic powder is the content of non-volatile matter. The non-volatile matter of the aesthetic additive for hydraulic compositions refers to the components that remain without volatilization after heating the aesthetic additive for hydraulic compositions in a hot air dryer at 105°C for 2 hours.

[0044] Other formulation conditions for the hydraulic composition according to this embodiment may be within the range of known formulation conditions for hydraulic compositions. For example, the ratio of water to the cement-containing binder (cement + admixture) (W / binder) may be 20% by mass or more and 70% by mass or less.

[0045] A hardened body can be obtained from the hydraulic composition according to this embodiment by a conventional construction method. That is, the hydraulic composition can be filled into a formwork or the like, and hardened precast concrete can be obtained through curing at room temperature or heating with steam.

[0046] The hydraulic composition according to this embodiment, by containing the above-mentioned aesthetic enhancement additive for hydraulic compositions, can improve aesthetics compared to the case where conventional aesthetic enhancement additives are included. This reduces the repair process for the cured body after manufacturing, improves production efficiency, and reduces manufacturing costs. Furthermore, it has the practical advantage of improving surface aesthetics by reducing the surface bubble occupancy rate of the cured hydraulic composition without affecting the amount of air in the hydraulic composition, compared to conventional aesthetic enhancement additives.

[0047] [Method of manufacturing precast concrete] The method for manufacturing precast concrete according to this embodiment comprises a hydraulic composition preparation step of mixing hydraulic powder, aggregate and water to prepare a hydraulic composition, and a filling step of filling a mold with the hydraulic composition, wherein in the hydraulic composition preparation step, the aesthetic additive for hydraulic composition is mixed in a ratio of more than 0 parts by mass and 2.0 parts by mass or less per 100 parts by mass of the hydraulic powder.

[0048] The method for manufacturing precast concrete according to this embodiment is simply to add the above-mentioned aesthetic additive for hydraulic compositions to an existing hydraulic composition, making it easy to manufacture a hydraulic composition that has improved surface aesthetics and reduces repair work.

[0049] [Other embodiments] Other embodiments of the aesthetic additive for hydraulic compositions, hydraulic compositions, precast concrete, and methods for producing precast concrete according to the present invention will be described. The configurations disclosed in each of the following embodiments can be applied in combination with configurations disclosed in other embodiments, provided that no inconsistencies arise.

[0050] One aspect of the present invention may be an aesthetic additive for hydraulic compositions containing the following ethyleneamine derivative (A). Ethyleneamine derivative (A): comprises at least one adduct obtained by directly adding propylene oxide to ethyleneamine, which is at least one of ethylenediamine and diethylenetriamine, and at least one block adduct obtained by further adding ethylene oxide to the adduct, wherein the total average number of moles of propylene oxide and ethylene oxide added per mole of ethyleneamine is 10 moles or more and 200 moles or less, and the ratio of the average number of moles of propylene oxide added to the total average number of moles of propylene oxide and ethylene oxide added is 40% or more and 100% or less.

[0051] One aspect of the present invention is a hydraulic composition for use in molding precast concrete, comprising hydraulic powder, aggregate, water, and an aesthetic additive for the hydraulic composition, wherein the content of the aesthetic additive for the hydraulic composition is greater than 0 parts by mass and 2.0 parts by mass or less per 100 parts by mass of the hydraulic powder.

[0052] One aspect of the present invention may be a precast concrete which is a hardened body of the above-mentioned hydraulic composition.

[0053] One aspect of the present invention is a method for manufacturing precast concrete, comprising: a hydraulic composition preparation step of mixing hydraulic powder, aggregate and water to prepare a hydraulic composition; and a filling step of filling a formwork with the hydraulic composition, wherein in the hydraulic composition preparation step, an aesthetic additive for the hydraulic composition is mixed in a ratio of more than 0 parts by mass and 2.0 parts by mass or less per 100 parts by mass of the hydraulic powder.

[0054] According to the above configuration, the occupancy rate of air bubbles on the surface of the hardened hydraulic composition can be reduced, thereby improving surface aesthetics. This reduces the repair process for the hardened material after manufacturing, and can improve production efficiency. The aesthetic enhancement additive of the present invention has excellent usability because it does not significantly affect the amount of air in the hydraulic composition when added.

[0055] One aspect of the present invention may be an aesthetic additive for a hydraulic composition in which the total average number of moles of propylene oxide and ethylene oxide added per mole of ethyleneamine is 40 moles or more and 150 moles or less.

[0056] This configuration further enhances surface aesthetics and is less likely to affect the air content of the hydraulic composition.

[0057] In the above embodiment, an example was described in which the aesthetic enhancement additive for hydraulic compositions was applied to a hydraulic composition of precast concrete. However, the aesthetic enhancement additive for hydraulic compositions of the present invention may also be used in hardened bodies of hydraulic compositions other than precast concrete. For example, the aesthetic enhancement additive for hydraulic compositions of the present invention may be applied to concrete manufactured at a construction site (especially exposed concrete, etc.).

[0058] With regard to other configurations, the embodiments disclosed herein are illustrative in all respects, and it should be understood that the scope of the present invention is not limited thereto. Those skilled in the art will readily understand that modifications can be made as appropriate without departing from the spirit of the invention. Therefore, other embodiments modified without departing from the spirit of the invention are naturally included within the scope of the present invention. [Examples]

[0059] The present invention will be further described below with reference to examples. However, the following examples are not limiting to the present invention.

[0060] [Preparation of aesthetic additives for hydraulic compositions] The compounds A-1 to A-18 and RA-1 to RA-6, which are used as aesthetic additives for hydraulic compositions, were produced using the following method. Compounds A-1 to A-18 are compounds corresponding to the ethyleneamine derivative (A) according to the present invention, while compounds RA-1 to RA-6 are compounds that do not correspond to the ethyleneamine derivative (A) according to the present invention.

[0061] (Raw material for ethyleneamine derivative (A)) The following materials were used as starting materials. Ethylenediamine-substituted compound (1): N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (reagent, manufactured by Merck KGaA) Ethylenediamine-substituted compound (2): N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (reagent, manufactured by Merck KGaA) Diethylenetriamine: Diethylenetriamine (reagent, manufactured by Merck KGaA) RA-6 does not use ethyleneamine as a starting material, but instead uses oleyl alcohol ("Angecol 85AN" (registered trademark, manufactured by Shin Nippon Rika Co., Ltd.)).

[0062] Ethyleneamine derivative (A) was synthesized by the following method. (Method for synthesizing A-1) 73.75 g of N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine and 0.50 g of potassium hydroxide were charged into a pressure vessel equipped with a stirrer, pressure gauge, and thermometer. The reaction system was then heated to 120°C, and the system was reduced to a reduced pressure for 1 hour to dehydrate it. Subsequently, while maintaining the reaction system at 135±5°C, 744.11 g of propylene oxide was added over 6 hours at a gauge pressure of 0.4 MPa. After aging for 0.5 hours at 135±5°C, 186.64 g of ethylene oxide was added over 4 hours at a gauge pressure of 0.4 MPa, and the reaction was terminated after 1 hour at 135±5°C. The resulting product was then neutralized with magnesium silicate ("Kyoward 600" (registered trademark, manufactured by Kyowa Chemical Industry Co., Ltd.)), filtered, and purified to obtain the purified product.

[0063] Analysis of the obtained compound A-1 using NMR and gel permeation chromatography (mass-average molecular weight in terms of polystyrene) confirmed that it is a compound obtained by sequentially adding 54.8 moles of propylene oxide and 16.8 moles of ethylene oxide to 1.0 mole of ethylenediamine.

[0064] (Method of combining A-2 to A-13, A-16, and A-17) The synthesis of each ethyleneamine derivative (A) was carried out in the same manner as the synthesis of A-1, except that the ratio of the starting materials (propylene oxide, ethylene oxide) was changed to obtain the ethyleneamine derivative (A) shown in Table 1.

[0065] (Method for synthesizing A-14) The starting material ratios (propylene oxide, ethylene oxide) were changed to obtain the ethyleneamine derivative (A) shown in Table 1. Since A-14 was an ethyleneamine PO adduct, ethylene oxide was not added. Therefore, in the synthesis of A-1 described above, after adding propylene oxide, the reaction was aged for 1 hour at 135±5°C before being terminated. Otherwise, the synthesis was carried out in the same manner as A-1.

[0066] (Method for synthesizing A-15) 23.63 g of diethylenetriamine was charged into a pressure vessel equipped with a stirrer, pressure gauge, and thermometer, and the system was purged with nitrogen. The reaction system was then heated to 90°C, and 53.22 g of propylene oxide was injected under nitrogen gas. The reaction was carried out at 120°C and a gauge pressure of 0.4 MPa for 1 hour. After cooling to 80°C and degassing, 0.50 g of potassium hydroxide was added to the reaction system, and the system was dehydrated under reduced pressure at 120°C for 1 hour. Subsequently, while maintaining the reaction system at 135±5°C, 665.27 g of propylene oxide was added over 6 hours at a gauge pressure of 0.4 MPa. After maintaining the temperature at 135±5°C for 0.5 hours for maturation, 262.37 g of ethylene oxide was added over 4 hours at a gauge pressure of 0.4 MPa, and the temperature at 135±5°C was maintained for 1 hour to complete the reaction. Subsequently, the obtained product was neutralized using magnesium silicate ("Kyoward 600" (registered trademark, manufactured by Kyowa Chemical Industry Co., Ltd.)), and then purified by filtration to obtain a purified product.

[0067] Analysis of the obtained compound A-15 using NMR and gel permeation chromatography (mass-average molecular weight in terms of polystyrene) confirmed that it is a compound obtained by sequentially adding 54.0 moles of propylene oxide and 26.0 moles of ethylene oxide to 1.0 mole of diethylenetriamine.

[0068] (Method of synthesizing A-18) Compound A-18 was synthesized in the same manner as compound A-15, except that the ratio of the raw materials was changed to obtain the ethyleneamine derivative (A) shown in Table 1.

[0069] (Synthesis method for RA-1) 65.53 g of N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine and 0.50 g of potassium hydroxide were charged into a pressure vessel equipped with a stirrer, pressure gauge, and thermometer. The reaction system was then heated to 120°C, and the system was reduced to a reduced pressure for 1 hour of dehydration. Subsequently, while maintaining the reaction system at 135±5°C, 781.01 g of propylene oxide and 157.96 g of ethylene oxide were added at a gauge pressure of 0.4 MPa over 8 hours. After the addition was complete, the system was maintained at 135±5°C for 1 hour to allow it to mature and complete the reaction. The resulting product was then neutralized with magnesium silicate ("Kyoward 600" (registered trademark, manufactured by Kyowa Chemical Industry Co., Ltd.)), and purified by filtration to obtain the purified product.

[0070] Analysis of the obtained compound RA-1 using NMR and gel permeation chromatography (mass-average molecular weight in terms of polystyrene) confirmed that it is a compound obtained by randomly adding 64.0 moles of propylene oxide and 16.0 moles of ethylene oxide to 1.0 mole of ethylenediamine.

[0071] (Synthesis method for RA-2) 63.72 g of N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine and 0.50 g of potassium hydroxide were charged into a pressure vessel equipped with a stirrer, pressure gauge, and thermometer. The reaction system was then heated to 120°C, and the system was reduced to a reduced pressure for 1 hour of dehydration. Subsequently, while maintaining the reaction system at 135±5°C, 95.03 g of ethylene oxide was added over 4 hours at a gauge pressure of 0.4 MPa. After 0.5 hours of maturation at 135±5°C, 845.75 g of propylene oxide was added over 6 hours at a gauge pressure of 0.4 MPa, and the reaction was terminated after 1 hour of maintaining 135±5°C. The resulting product was then neutralized with magnesium silicate ("Kyoward 600" (registered trademark, manufactured by Kyowa Chemical Industry Co., Ltd.)), filtered, and purified to obtain the purified product.

[0072] Analysis of the obtained compound RA-2 using NMR and gel permeation chromatography (mass-average molecular weight in terms of polystyrene) confirmed that it is a compound obtained by sequentially adding 12.0 moles of ethylene oxide and 54.0 moles of propylene oxide to 1.0 mole of ethylenediamine.

[0073] (Synthesis method for RA-3) RA-3 was synthesized in the same manner as RA-2, except that the ratio of the raw materials was changed to obtain the ethyleneamine derivatives shown in Table 1.

[0074] (Synthesis method for RA-4 and RA-5) RA-4 and RA-5 were synthesized in the same manner as A-1, except that the ratio of the raw materials was changed to obtain the ethyleneamine derivatives shown in Table 1.

[0075] (Synthesis method for RA-6) 141.0 g of oleyl alcohol and 0.90 g of potassium hydroxide were charged into a pressure vessel equipped with a stirrer, pressure gauge, and thermometer. The reaction system was then heated to 110°C, and the system was reduced to a reduced pressure for 1 hour to dehydrate it. Subsequently, while maintaining the reaction system at 110±5°C, 94.85 g of ethylene oxide was added over 1 hour at a gauge pressure of 0.4 MPa. After aging for 0.5 hours at 135±5°C, 768.65 g of propylene oxide was added over 5 hours at a gauge pressure of 0.4 MPa, and the reaction was terminated after maintaining the temperature at 135±5°C for 1 hour. The resulting product was then neutralized using magnesium silicate ("Kyoward 600" (registered trademark, manufactured by Kyowa Chemical Industry Co., Ltd.)), and purified by filtration to obtain a purified product.

[0076] Analysis of the obtained compound RA-6 using NMR and gel permeation chromatography (mass-average molecular weight in terms of polystyrene) confirmed that it is a compound obtained by sequentially adding 4.1 moles of ethylene oxide and 25.2 moles of propylene oxide to 1.0 mole of oleyl alcohol.

[0077] Furthermore, NMR is performed using an NMR spectrometer (Varian Mercury 300 (300MHz)) to analyze radionuclides. 1 H, 13 This measurement was taken using C and the solvent CDCl3. Furthermore, gel permeation chromatography was performed under the following measurement conditions. <Measurement conditions for gel permeation chromatography> Equipment: HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK gel Super H4000 + TSK gel Super H3000 + TSK gel Super H2000 (manufactured by Tosoh Corporation) Detector: Differential refractometer (RI) Eluent: Tetrahydrofuran Flow rate: 0.5mL / min Column temperature: 40℃ Sample concentration: 0.5% by mass eluent solution Standard material: Polystyrene (manufactured by Tosoh Corporation)

[0078] By the above method, compounds A-1 to A-18 and RA-1 to RA-6 shown in Table 1 were obtained. [Table 1]

[0079] [Concrete Testing] Next, using the aesthetic additives for hydraulic compositions produced by the method described above, hydraulic compositions for concrete were prepared for each of Examples 1 to 20 and Comparative Examples 1 to 7, and precast concrete was produced. Compounds A-1 to A-18 and RA-1 to RA-6 were used after being mixed with mixing water, as described later. Various evaluation tests were also conducted on the concrete during and after its production for each of the Examples and Comparative Examples.

[0080] (Method for preparing a hydraulic composition) In a 50L nominal capacity twin-shaft forced mixer, the following mixing conditions were used: Blast furnace cement type B (equal mixture of cements from Taiheiyo Cement Corporation, Ube Mitsubishi Cement Corporation, and Sumitomo Osaka Cement Corporation, with a density of 3.04 g / cm³) was used as the hydraulic powder (cement) according to the mixing conditions listed in the table below. 3 Fine aggregate (land sand from the Oi River system, density 2.60 g / cm³), coarse aggregate (crushed stone from Okazaki, density 2.66 g / cm³) 3 The ingredients were added sequentially and the mixture was dry-mixed for 10 seconds. In Table 2, W / C indicates the mass ratio of water to cement, and s / a indicates the fine aggregate ratio. Tap water from Gamagori City was used as the water.

[0081] [Table 2]

[0082] Next, a cement dispersant (Takemoto Oil & Fat Co., Ltd.'s high-performance water-reducing agent for products "Tupole NV-80" (registered trademark, polycarboxylic acid-based dispersant)), the aesthetic additive for hydraulic compositions shown in Table 1, an air-entraining agent (Takemoto Oil & Fat Co., Ltd.'s AE-200 (product name)), and an antifoaming agent (Takemoto Oil & Fat Co., Ltd.'s AFK-2 (product name)) were added to the mixing water. The cement dispersant, aesthetic additive, air-entraining agent, and antifoaming agent were considered part of the mixing water and added together with the mixing water, then mixed for 90 seconds (the mixing volume was 25L). The amount of cement dispersant added was such that the fresh concrete had the desired fluidity (specifically, a slump of 18±2.5cm). The amount of aesthetic additive for hydraulic compositions (non-volatile content) added was set to 0 to 2.0 parts by mass per 100 parts by mass of cement, the amount of air-entraining agent added was set to 0.002 to 0.2 parts by mass per 100 parts by mass of cement, and the amount of defoaming agent added was set to 0.0005 parts by mass or 0.1 parts by mass per 100 parts by mass of cement, with these components added as part of the mixing water. In addition, the addition rates of the air-entraining agent and defoaming agent were adjusted as appropriate so that the finished concrete had the desired amount of air (4.5 ± 0.5%).

[0083] The obtained hydraulic compositions were subjected to slump tests in accordance with JIS A 1101:2020. For both the examples and comparative examples, the slump value was within the range of 18 ± 2.5 cm, confirming that it was within the desired fluidity range. Furthermore, the air content of the obtained hydraulic compositions was measured according to JIS A 1128:2020. For both the examples and comparative examples, it was confirmed that the air content was within the target range. Since the slump and air content were equivalent in each example and comparative example, the influence of these factors can be excluded when comparing the aesthetic improvement and air content of the hydraulic compositions for each example. In other words, experimental conditions were established to examine the differences in aesthetic improvement and air content due to differences in the aesthetic additives used for hydraulic compositions. In this manner, hydraulic compositions of Examples 1-20 and Comparative Examples 1-7 were prepared under different manufacturing conditions.

[0084] [Method for preparing a hardened hydraulic composition (test specimen)] After mixing, each hydraulic composition from the Examples and Comparative Examples was poured in a single operation using a jug into a bottomed cylindrical steel mold with an inner diameter of 10 cm and a height of 20 cm. Then, the mold was vibrated using a table vibrator (vibration frequency 2800 vpm) for 30 seconds, and the mold was left to stand in a constant temperature room at 20°C and 80% humidity. After 24 hours, the hardened concrete was removed from the mold, and hardened hydraulic compositions (test specimens, equivalent to precast concrete) for each example and comparative example were prepared.

[0085] The following evaluations were performed on the hardened hydraulic compositions (test specimens) of each example and comparative example obtained.

[0086] (Evaluation of the degree of improvement in aesthetics) The aesthetic improvement of the obtained hydraulic composition hardened body was evaluated by measuring the surface bubble occupancy rate. In detail, the surface bubble occupancy rate was measured by scanning the side surface (cylindrical curved surface) of the obtained cylindrical hardened concrete body with a handheld scanner (Sanwa Direct "400-SCN032", resolution 900 dpi). The scanned image was binarized using bitmap image editing and processing software "GIMP 2.10.20" to separate the "bubble marks" recognized as black from the "non-bubble marks" recognized as white. Subsequently, the area ratio (%) of the part corresponding to the bubble marks relative to the entire side surface of the hardened concrete body in the scanned image was calculated as the surface bubble occupancy rate, and the surface aesthetics were evaluated. The threshold for binarization was set so that the number of bubble marks in the processed image was the same as the number of bubble marks in the original scanned image. At this time, the formwork boundary lines remaining on the hardened concrete body were sometimes recognized as black, but these parts were deleted and made white.

[0087] Comparative Example 7, which does not contain an aesthetic additive for hydraulic compositions, was used as the reference sample. With the surface bubble occupancy of Comparative Example 7 set to 100%, the surface bubble occupancy of each example and comparative example was evaluated as the surface bubble occupancy relative to the reference sample according to the following evaluation criteria.

[0088] (Evaluation criteria for improving aesthetics) S: The surface bubble occupancy rate relative to the reference sample is 30% or less. A: The surface bubble occupancy rate relative to the reference sample is greater than 30% but less than or equal to 50%. B: The surface bubble occupancy rate relative to the reference sample is greater than 50% but less than or equal to 80%. C: The surface bubble occupancy rate relative to the reference sample is greater than 80% but less than or equal to 95%. D: The surface bubble occupancy rate exceeds 95% relative to the reference sample.

[0089] (Evaluation of the impact on air volume) The following formula was used to calculate the increase in air-entraining agent and antifoaming agent for each example and comparative example, relative to the reference sample, Comparative Example 7. Increase in air-entraining agent = (Amount of air-entraining agent added per 100 parts by mass of hydraulic powder in each example and comparative example (parts by mass)) - (Amount of air-entraining agent added per 100 parts by mass of hydraulic powder in Comparative Example 7 (parts by mass)) Increase in defoaming agent = (Amount of defoaming agent added per 100 parts by mass of hydraulic powder in each example and comparative example (parts by mass)) - (Amount of defoaming agent added per 100 parts by mass of hydraulic powder in Comparative Example 7 (parts by mass)) Furthermore, the effect of increasing the amount of air-entraining agent and the amount of antifoaming agent on the amount of air in the hydraulic composition was evaluated according to the following criteria.

[0090] (Evaluation criteria for the impact on air volume) S: Both the increase in air-entraining agent and the increase in antifoaming agent are between 0 and 0.01. A: Either the increase in air-entraining agent or the increase in antifoaming agent, or both, are greater than 0.01 and less than or equal to 0.03. B: Either the increase in air-entraining agent or the increase in antifoaming agent, or both, are greater than 0.03 and less than or equal to 0.10. C: Either the increase in air-entraining agent or the increase in antifoaming agent, or both, exceeds 0.10.

[0091] Table 3 shows the formulation conditions and evaluation results for the hydraulic compositions in each example and comparative example. [Table 3]

[0092] As shown in Examples 1 to 20, the hydraulic compositions to which the aesthetic enhancement additive containing the ethyleneamine derivative (A) of the present invention was added all received an aesthetic enhancement rating of C or higher and an impact on air content rating of B or higher, demonstrating that concrete test specimens with improved aesthetics could be produced while suppressing the impact on air content. In contrast, Comparative Examples 1 to 7, which did not contain the ethyleneamine derivative (A) of the present invention, could not achieve both improved aesthetics and an impact on air content. Among Examples 1 to 20, Examples 1 to 14, which used ethyleneamine derivatives (A) A-1 to A-12 as an aesthetic additive, were particularly excellent, with an aesthetic improvement rating of S or higher and an impact on air volume rating of A or higher, or an aesthetic improvement rating of A or higher and an impact on air volume rating of S or higher. These derivatives were ethyleneamine derivatives (A) obtained by directly adding propylene oxide (PO) to ethylenediamine, and further adding ethylene oxide (EO) to an adduct, where the average total number of added moles of propylene oxide (PO) and ethylene oxide (EO) per mole of ethyleneamine was between 40 moles and 150 moles, and the ratio of the average number of added moles of propylene oxide (PO) to the total average number of added moles of propylene oxide (PO) and ethylene oxide (EO) was between 60% and 95%. [Industrial applicability]

[0093] This invention can be applied to hydraulic compositions such as concrete.

Claims

1. An aesthetic additive for hydraulic compositions, characterized by containing the following ethyleneamine derivative (A) and being used in hydraulic compositions for forming precast concrete or cast-in-place concrete molded in a formwork. Ethyleneamine derivative (A): The present invention comprises at least one adduct obtained by directly adding propylene oxide to ethyleneamine, which is at least one of ethylenediamine and diethylenetriamine, and at least one block adduct obtained by further adding ethylene oxide to the adduct, The total average number of moles of propylene oxide and ethylene oxide added per mole of ethyleneamine is 60 moles or more and 100 moles or less, and the ratio of the average number of moles of propylene oxide added to the total average number of moles of propylene oxide and ethylene oxide added is 40% or more and 100% or less.

2. The aesthetic additive for hydraulic compositions according to claim 1, wherein the ethyleneamine comprises ethylenediamine.

3. The aesthetic additive for a hydraulic composition according to claim 1, wherein the ratio of the average number of moles of propylene oxide added to the total average number of moles of propylene oxide and ethylene oxide added is 60% or more and 95% or less.

4. A hydraulic composition for use in molding precast concrete or cast-in-place concrete formed with formwork, A hydraulic composition comprising hydraulic powder, aggregate, water, and an aesthetic additive for hydraulic compositions according to any one of claims 1 to 3, wherein the content of the aesthetic additive for hydraulic compositions is greater than 0 parts by mass and less than or equal to 2.0 parts by mass per 100 parts by mass of hydraulic powder.

5. The hydraulic composition according to claim 4, further comprising an air-entraining agent.

6. A concrete characterized by being a hardened body of the hydraulic composition according to claim 4, which is precast concrete or cast-in-place concrete.

7. A hydraulic composition preparation step involves mixing hydraulic powder, aggregate, and water to prepare a hydraulic composition. A method for manufacturing concrete, comprising a filling step of filling a formwork with the hydraulic composition, wherein the concrete is precast concrete or cast-in-place concrete, A method for producing concrete, characterized in that, in the step of preparing the hydraulic composition, an aesthetic additive for hydraulic compositions containing the following ethyleneamine derivative (A) is mixed in a ratio of more than 0 parts by mass and 2.0 parts by mass or less per 100 parts by mass of the hydraulic powder. Ethyleneamine derivative (A): The present invention comprises at least one adduct obtained by directly adding propylene oxide to ethyleneamine, which is at least one of ethylenediamine and diethylenetriamine, and at least one block adduct obtained by further adding ethylene oxide to the adduct, The total average number of moles of propylene oxide and ethylene oxide added per mole of ethyleneamine is 10 moles or more and 200 moles or less, and the ratio of the average number of moles of propylene oxide added to the total average number of moles of propylene oxide and ethylene oxide added is 40% or more and 100% or less.

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