Strength enhancers for hydraulic components, mixtures for hydraulic components, hydraulic components, and hydraulic component hardeners.

Abstract

To provide a strength enhancing agent for a hydraulic composition, capable of developing high compressive strength in an early stage as well as maintaining strength development property after passage of an extended period.SOLUTION: Disclosed is a strength enhancing agent for a hydraulic composition to be used in a hydraulic composition involving a hydraulic binder. The strength enhancing agent for a hydraulic composition is characterized by involving diethylene glycol as a component A and glycerin as a component B.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a strength enhancer for hydraulic compositions, an admixture for hydraulic compositions, a hydraulic composition, and a cured hydraulic composition. More specifically, the present invention relates to a strength enhancer for hydraulic compositions that can exhibit high compressive strength early in the curing process of a hydraulic composition while maintaining strength development over a long period of time, an admixture for hydraulic compositions containing the same, a hydraulic composition containing the strength enhancer or admixture, and a cured hydraulic composition formed from the hydraulic composition. [Background technology]

[0002] Conventionally, hydraulic compositions, such as concrete, are composed of cement, water, fine aggregate, coarse aggregate, and admixtures for hydraulic compositions. Of these, the admixtures for hydraulic compositions contain dispersion components, mainly composed of polycarboxylic acid copolymers, from the viewpoint of increasing the fluidity of the hydraulic composition.

[0003] In the production of precast concrete products, early demolding is required to improve productivity. Similarly, in outdoor concrete placement, early hardening is also required. In particular, in cold regions, it takes a long time for placed concrete to harden sufficiently, so there is a high demand for early hardening. For these reasons, strength enhancers (see, for example, Patent Documents 1-3) are added to admixtures to shorten the time required for hardening.

[0004] Specifically, Patent Document 1 discloses a cement strength enhancer that minimizes the decrease in fluidity of the cement composition and can exhibit high compressive strength at an early age. Patent Document 2 discloses a strength enhancer composition for hydraulic powders that yields a hardened body with high initial strength. Patent Document 3 discloses a rapid strengthening agent for hydraulic compositions that exhibits excellent short-term strength improvement effects. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2006-282414 [Patent Document 2] Japanese Patent Publication No. 2014-189417 [Patent Document 3] Japanese Patent Publication No. 2009-256201 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] However, the strength enhancers described in Patent Documents 1-3 had room for further improvement. Specifically, conventionally, there was a trade-off between early strength development and long-term strength development, making it difficult to achieve high compressive strength early on while maintaining strength development over a long period. Therefore, there was a need to develop a strength enhancer that could exhibit high strength development early on while maintaining strength development over a long period.

[0007] Therefore, in view of the above circumstances, the object of the present invention is to provide a strength enhancer for hydraulic compositions that can exhibit high compressive strength early during the hardening of the hydraulic composition while maintaining strength development even after a long period of time. [Means for solving the problem]

[0008] The present inventors, through diligent research to solve the above problems, have found that the above problems can be solved by including both diethylene glycol (component A) and glycerin (component B). According to the present invention, the following strength enhancer for hydraulic compositions, admixture for hydraulic compositions, hydraulic compositions, and cured hydraulic compositions are provided.

[0009] [1] Strength enhancer for hydraulic compositions used in hydraulic compositions containing a hydraulic binder, Contains the following components A and B. death, Furthermore, it contains at least one selected from the following components C, D, E, and F. The mass ratio of component A and component B is A / B = 1.5 / 1 to 5 / 1. A strength enhancer for hydraulic compositions, characterized by the following. Component A: Diethylene glycol. Component B: Glycerol. Component C: Nitrogen-containing organic compound with a molecular weight of 500 or less. Component D: Sulfur-containing organic compound with a molecular weight of 500 or less. Component E: Divalent to tetravalent polyhydric alcohols with a molecular weight of 500 or less (excluding those corresponding to components A, B, C, D, and sugars). The aforementioned E component is, Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,2,4-butanetriol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2- It is at least one selected from the group consisting of cyclopentanediol, 1,3-cyclopentanediol, 1,4-cyclopentanediol, 1,2,5-pentanetriol, triethylene glycol, tetraethylene glycol, pinacol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, dipropylene glycol, tripropylene glycol, trimethylolpropane, and diglycerin. Component F: A carbonate ester compound with a molecular weight of 500 or less.

[0010] (delete)

[0011] (delete)

[0012] 2 Containing at least two selected from the group consisting of said Component C, said Component D, said Component E, and said Component F, the strength enhancer for hydraulic compositions according to 1 described above.

[0013] 3 Containing at least three selected from the group consisting of said Component C, said Component D, said Component E, and said Component F, the strength enhancer for hydraulic compositions according to 1 or 2 described above.

[0014] 4 When the total content ratio of said Component A, said Component B, said Component C, said Component D, said Component E, and said Component F is 100 parts by mass, Containing said Component A and said Component B in a total of 55 to 99 parts by mass, and said Component C, said Component D, said Component E, and said Component F in a total of 1 to 45 parts by mass, the strength enhancer for hydraulic compositions according to 1 to 3 described above.

[0015] 5 Said [1] to 4 ​​​​An admixture for hydraulic compositions characterized by containing a strength enhancer for hydraulic compositions and a dispersant as described in any of the [ ].

[0016] [ 6 ] The above [ 5 A hydraulic composition characterized by containing the admixture for hydraulic compositions described in [ ].

[0017] [ 7 ] The above [1]~[ 4 A hydraulic composition characterized by containing a strength enhancer for hydraulic compositions as described in any of the following.

[0018] [ 8 ] The above [ 6 ]or[ 7 A cured hydraulic composition characterized by being a cured product of the hydraulic composition described in [ ]. [Effects of the Invention]

[0019] The strength enhancer for hydraulic compositions of the present invention has the effect of enabling the hydraulic composition to exhibit high compressive strength early in the curing process, while also maintaining its strength even after a long period of time.

[0020] The hydraulic composition admixture of the present invention, by containing the strength enhancer for hydraulic compositions of the present invention, has the effect of enabling the hydraulic composition to exhibit high compressive strength early during hardening, while also maintaining strength development even after a long period of time.

[0021] The hydraulic composition of the present invention, by containing the admixture for hydraulic compositions of the present invention, exhibits the effect of developing high compressive strength early during hardening while maintaining strength development even after a long period of time.

[0022] The hydraulic composition cured body of the present invention is formed using the hydraulic composition of the present invention and exhibits the effect of high compressive strength in the early stages of curing, as well as maintaining strength development even after a long period of time. [Modes for carrying out the invention]

[0023] Embodiments of the present invention will be described below. However, the present invention is not limited to the following embodiments. Therefore, it should be understood that, without departing from the spirit of the present invention, appropriate modifications and improvements may be made to the following embodiments based on the ordinary knowledge of those skilled in the art. In the following examples, unless otherwise stated, % means mass%, and parts means parts by mass.

[0024] (1) Strength enhancers for hydraulic compositions: The strength enhancer for hydraulic compositions of the present invention is a strength enhancer for hydraulic compositions used in hydraulic compositions containing a hydraulic binder, and contains the following component A and the following component B. Component A: Diethylene glycol. Component B: Glycerin.

[0025] Such strength enhancers for hydraulic compositions can induce high compressive strength early in the hardening process of hydraulic compositions (e.g., 24 to 48 hours after curing) while also maintaining strength development over a long period (e.g., around 28 days after curing).

[0026] Here, there is a trade-off between the early strength development during the curing of a hydraulic composition and the strength development after a long period of time. Conventional strength enhancers make it difficult to achieve both high strength development early and high strength development after a long period of time. In other words, with conventional strength enhancers, if high compressive strength is achieved early, strength development after a long period of time is low, and if strength development after a long period of time is high, early compressive strength is difficult to achieve. On the other hand, the strength enhancer for hydraulic compositions of the present invention makes it possible to sufficiently achieve both early compressive strength and strength development after a long period of time.

[0027] In this invention, the details of the mechanism by which the hydraulic composition exhibits high strength development early on while maintaining strength development over a long period of time are unknown, but it is presumed to be as follows. Generally, the components of cement do not undergo hydration in an orderly manner, but rather each component reacts with the others in a complex manner as hydration progresses and hardens. Therefore, adding only a single component results in an uneven progression of hydration. That is, the progression of hydration improves only partially, and in some areas, the progression of hydration decreases, so it is thought that the hardened body as a whole does not exhibit sufficient strength. However, by combining components A and B of this invention, the uneven progression of hydration is eliminated, and it is thought that high strength development early on can be achieved while maintaining strength development over a long period of time. In particular, by employing components with different functional groups, such as components C, D, E, and F, the above effect will be exhibited even more favorably.

[0028] Furthermore, the strength enhancer for hydraulic compositions of the present invention exhibits good compatibility with dispersants, and high formulation stability is achieved in admixtures for hydraulic compositions containing the strength enhancer for hydraulic compositions of the present invention and a dispersant.

[0029] (1-1) Components A and B: The present invention contains both diethylene glycol and glycerin. By containing both diethylene glycol and glycerin in this way, their combined effects enable the early development of high compressive strength, and furthermore, the strength development can be maintained even after a long period of time.

[0030] There are no particular restrictions on the mass ratio of component A and component B, but it is preferable that component A / component B = 1 / 1 to 5 / 1. In this invention, the ratio is 1.5 / 1 to 5 / 1. A ratio of 1.5 / 1 to 3.5 / 1 is even more preferable. By setting the ratio within this range, particularly high compressive strength can be achieved early in the curing of the hydraulic composition, and furthermore, the strength development after a long period of time can be better maintained.

[0031] (1-2) Components C, D, E, and F: The strength enhancer for hydraulic compositions of the present invention further contains at least one selected from the following components C, D, E, and F. ru. By including one or more of these components, it is possible to achieve particularly high compressive strength early in the curing process of the hydraulic composition, and furthermore, to maintain the strength development even after a long period of time. Component C: Nitrogen-containing organic compound with a molecular weight of 500 or less. Component D: Sulfur-containing organic compound with a molecular weight of 500 or less. Component E: Divalent to tetravalent polyhydric alcohols with a molecular weight of 500 or less (excluding components A, B, C, D, and sugars). However, in this invention, component E is at least one selected from the group consisting of the following: Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,2,4-butanetriol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,2,4-trimethyl-1,3- Pentanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,4-cyclopentanediol, 1,2,5-pentanetriol, triethylene glycol, tetraethylene glycol, pinacol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, dipropylene glycol, tripropylene glycol, trimethylolpropane, diglycerin Component F: A carbonate ester compound with a molecular weight of 500 or less.

[0032] Component C is a nitrogen-containing organic compound with a molecular weight of 500 or less. There are no particular restrictions on the lower limit of this molecular weight; it can be the same as the nitrogen-containing organic compound with the theoretically smallest molecular weight among nitrogen-containing organic compounds. Specifically, the lower limit of the molecular weight of this nitrogen-containing organic compound can be set to 31.

[0033] Component C can specifically include tris(hydroxymethyl)aminomethane, diethanolamine, methyldiethanolamine, triethanolamine, diisopropanolamine, methyldiisopropanolamine, triisopropanolamine, diethanolisopropanolamine, ethanoldiisopropanolamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 2-aminoethanol, 2-(methylamino)ethanol, 1-amino-2-propanol, 2-amino-1-propanol, 2-amino-2-methyl-1-propanol, 1,3-diamino-2-propanol, 1-amino-2-butanol, 2-amino-1-butanol, 2-amino-2-ethyl-1,3-propanediol, and 2-(2-aminoethoxy)ethanol.

[0034] The C component may be used alone or in combination of two or more types.

[0035] Component D is a sulfur-containing organic compound with a molecular weight of 500 or less. There are no particular restrictions on the lower limit of this molecular weight; it can be the same as the sulfur-containing organic compound with the theoretically smallest molecular weight among sulfur-containing organic compounds. Specifically, the lower limit of the molecular weight of this sulfur-containing organic compound can be 94.

[0036] Component D specifically includes dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, 2-hydroxyethyl methyl sulfone, isopropyl methyl sulfone, ethyl phenyl sulfone, tetramethylene sulfone, 4,4-dioxo-1,4-oxatian, methanesulfonic acid, hydroxymethanesulfonic acid, ethylsulfonic acid, aminomethanesulfonic acid, 2-hydroxyethanesulfonic acid, 2-aminoethanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, 4-hydroxybenzenesulfonic acid, aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, toluidinesulfonic acid, cresolsulfonic acid, methanesulfinic acid, hydroxymethanesulfinic acid, dicyclohexylsulfosuccinic acid, and their alkali metal salts and alkaline earth metal salts.

[0037] Component D may be used alone or in combination of two or more types.

[0038] Component E is a divalent to tetravalent polyhydric alcohol with a molecular weight of 500 or less (excluding components A, B, C, D, and sugars). There is no particular restriction on the lower limit of this molecular weight; it can be the same as the divalent to tetravalent polyhydric alcohol with the smallest theoretical molecular weight among the above polyhydric alcohols. For example, the lower limit of the molecular weight of the above polyhydric alcohol can be 62.

[0039] Component E specifically includes ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,2,4-butanetriol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2,4-dimethyl-1,5-pentanediol, and 2,2,4-trimethyl-1,3- Examples include pentanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,4-cyclopentanediol, 1,2,5-pentanetriol, triethylene glycol, tetraethylene glycol, pinacol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, dipropylene glycol, tripropylene glycol, trimethylolpropane, and diglycerin.

[0040] Component E may be used alone or in combination of two or more types.

[0041] Component F is a carbonate ester compound with a molecular weight of 500 or less. There are no particular restrictions on the lower limit of this molecular weight; it can be the same as the carbonate ester compound with the theoretically smallest molecular weight among carbonate ester compounds. For example, the lower limit of the molecular weight of the carbonate ester compound can be 88.

[0042] Specific examples of component F include glycerol-1,2-carbonate, ethylene carbonate, propylene carbonate, dimethyl 2,5-dioxahexanediate, dimethyl carbonate, diethyl carbonate, 1,3-dioxan-2-one, and ethyl methyl carbonate.

[0043] The F component may be used alone or in combination of two or more types.

[0044] The strength enhancer for hydraulic compositions of the present invention more preferably contains at least two selected from components C, D, E, and F, and particularly preferably contains at least three selected from components C, D, E, and F. It is preferable to include multiple components from C, D, E, and F in this way, as this allows for the early development of particularly high compressive strength during the curing of the hydraulic composition, and furthermore, the strength development after a long period of time can be better maintained.

[0045] If the total content of components A, B, C, D, E, and F is 100 parts by mass, it is preferable that components A and B are included in a total of 55 to 99 parts by mass, and components C, D, E, and F are included in a total of 1 to 45 parts by mass. Furthermore, it is even more preferable that components A and B are included in a total of 60 to 90 parts by mass, and components C, D, E, and F are included in a total of 10 to 40 parts by mass, and it is particularly preferable that components A and B are included in a total of 65 to 85 parts by mass, and components C, D, E, and F are included in a total of 15 to 35 parts by mass. By blending in these proportions, it is possible to achieve particularly high compressive strength early in the curing of the hydraulic composition, and furthermore, to maintain the strength development even after a long period of time.

[0046] (1-3) Other components: The strength enhancer for hydraulic compositions of the present invention may further contain other components in addition to components A, B, C, D, E, and F.

[0047] Other components include conventionally known strength enhancers (component G) such as sodium nitrite, calcium nitrite, sodium nitrate, calcium nitrate, sodium sulfite, calcium sulfite, lithium sulfate, sodium sulfate, potassium sulfate, sodium carbonate, sodium bicarbonate, and calcium formate.

[0048] As for the content ratio of other components, for example, it can be 0 to 10 parts by mass, preferably 0 to 5 parts by mass, relative to 100 parts by mass of the total amount of components A to F.

[0049] The strength enhancer for hydraulic compositions of the present invention is used when preparing a hydraulic composition by adding mixing water to a binder (hydraulic binder).

[0050] (2) Admixtures for hydraulic compositions: The hydraulic composition admixture of the present invention contains the hydraulic composition strength enhancer and dispersant of the present invention. By containing the hydraulic composition strength enhancer of the present invention, such a hydraulic composition admixture can exhibit high compressive strength early in the curing of the hydraulic composition, and furthermore, maintain strength development even after a long period of time. In addition, the hydraulic composition strength enhancer of the present invention has good compatibility with the dispersant, and the hydraulic composition admixture of the present invention exhibits good formulation stability when in aqueous solution.

[0051] There are no particular restrictions on the mixing ratio of the strength enhancer for hydraulic compositions and the dispersant (strength enhancer for hydraulic compositions / dispersant), and it can be set as appropriate. For example, it can be set to 0.25 to 4, and it is preferable to set it to 0.5 to 2.5.

[0052] There are no particular restrictions on the dispersant, and any dispersant used in conventionally known admixtures for hydraulic compositions can be appropriately selected. Examples of dispersants include polycarboxylic acid copolymers, phosphate ester copolymers, naphthalene condensates, melamine condensates, phenol condensates, and lignin sulfonates.

[0053] The admixture for hydraulic compositions of the present invention may further contain other additives in addition to the strength enhancer and dispersant for hydraulic compositions of the present invention.

[0054] Other additives are not particularly limited and may be included as appropriate, as long as the effectiveness is not impaired. Examples of such other additives include coagulation retarders consisting of sugars or oxycarboxylates, air-enhancing agents consisting of anionic surfactants, defoaming agents consisting of oxyalkylene compounds, shrinkage reducing agents consisting of polyoxyalkylene alkyl ethers, thickeners consisting of cellulose ether compounds, preservatives consisting of isothiazolinone compounds, and rust inhibitors consisting of nitrites.

[0055] The content of other additives can be, for example, 0 to 20% by mass in the admixture for hydraulic compositions.

[0056] (3) Hydraulic composition: In its first embodiment, the hydraulic composition of the present invention contains the admixture for hydraulic compositions of the present invention.

[0057] Furthermore, a second embodiment of the hydraulic composition of the present invention contains a strength enhancer for hydraulic compositions of the present invention. In other words, instead of an admixture for hydraulic compositions as in the first embodiment, the strength enhancer for hydraulic compositions may be directly incorporated.

[0058] Such hydraulic compositions, by containing the admixture for hydraulic compositions or the strength enhancer for hydraulic compositions of the present invention, exhibit high compressive strength early during the curing of the hydraulic composition, while also maintaining strength development even after a long period of time.

[0059] The hydraulic composition of the present invention may contain a binder (hydraulic binder), water, fine aggregate, and coarse aggregate, similar to conventionally known hydraulic compositions.

[0060] The hydraulic composition of the present invention is not particularly limited in terms of the content ratio of the admixture for the hydraulic composition of the present invention or the strength enhancer for the hydraulic composition of the present invention, and can be set as appropriate. For example, the content ratio of the admixture for the hydraulic composition of the present invention can be 0.01 to 3.0 parts by mass per 100 parts by mass of the binder. Similarly, the content ratio of the strength enhancer for the hydraulic composition of the present invention can be 0.01 to 1.5 parts by mass per 100 parts by mass of the binder.

[0061] Examples of binders 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 various types of cement such as blast furnace cement, fly ash cement, and silica fume cement.

[0062] Furthermore, various admixtures such as fly ash, blast furnace slag powder, limestone powder, stone powder, silica fume, and expansives may be used in combination as binders.

[0063] Examples of fine aggregates include river sand, mountain sand, land sand, sea sand, silica sand, crushed sand, and various slag aggregates, but they may also contain fine particles such as clay.

[0064] Examples of coarse aggregates include river gravel, mountain gravel, land gravel, crushed stone, various types of slag coarse aggregates, and lightweight aggregates.

[0065] The hydraulic composition of the present invention may further contain other admixtures as appropriate, within a range that does not impair its effectiveness. Examples of such other admixtures include setting retarders consisting of sugars or oxycarboxylates, various water-reducing agents, AE agents consisting of anionic surfactants, defoaming agents consisting of oxyalkylene compounds, curing accelerators consisting of alkanolamines, shrinkage reducing agents consisting of polyoxyalkylene alkyl ethers, thickeners consisting of cellulose ether compounds, rapid setting agents consisting of calcium sulfonates, preservatives consisting of isothiazolinone compounds, and rust inhibitors consisting of nitrites.

[0066] The content ratio of other admixtures can be, for example, 0 to 5 parts by mass per 100 parts by mass of binder.

[0067] The hydraulic composition of the present invention can appropriately adopt conventionally known ratios for the ratio of water to binder (water / binder ratio), for example, it can be 20 to 70% by mass.

[0068] By filling this hydraulic composition into a mold or the like and curing it at room temperature or by heating with steam, hardened mortar, concrete, etc. can be obtained.

[0069] (4) Cured hydraulic composition: The cured hydraulic composition of the present invention is a cured product of the hydraulic composition of the present invention. This cured hydraulic composition is formed from the hydraulic composition of the present invention, exhibits high compressive strength in the early stages of curing, and maintains strength development even after a long period of time.

[0070] Hydraulic composition hardened bodies specifically refer to hardened mortar (hardened mortar) and hardened concrete (hardened concrete), among others. [Examples]

[0071] The present invention will be described in detail below based on examples, but the present invention is not limited to these examples.

[0072] First, Table 1 below shows the components C to G used in the examples and comparative examples.

[0073] [Table 1]

[0074] (Example 1~ 73、75~ 94. Comparative Examples 1-9 , Reference example 74 ) (1) Preparation of strength enhancers for hydraulic compositions: Strength enhancers for hydraulic compositions (X-1 to X-76) were prepared by blending component A (diethylene glycol, abbreviated as "DEG" in Table 2 (Tables 2-1 to 2-3)), component B (glycerin), and components C to G in the types and amounts shown in Table 2 (Tables 2-1 to 2-3).

[0075] [Table 2-1]

[0076] [Table 2-2]

[0077] [Table 2-3]

[0078] Next, Table 3 (Tables 3-1 to 3-3) below shows the various mixing ratios for components A to F. However, if the content of component A or B is "0", "-" is written in the "Component A / Component B Mass Ratio" column.

[0079] [Table 3-1]

[0080] [Table 3-2]

[0081] [Table 3-3]

[0082] (2) Preparation of hydraulic composition (mortar): Next, the hydraulic composition of Example 1 was prepared as follows.

[0083] First, using a mechanical mixer specified in JIS R5201, mix ordinary Portland cement (manufactured by Taiheiyo Cement Corporation, density 3.16 g / cm³) according to the formulation (mortar formulation) shown in Table 4. 3 ), blast furnace slag fine powder #4000 (manufactured by Esment Chubu Co., Ltd., density 2.88 g / cm³) 3 ), fine aggregate (Oigawa River system land sand, density 2.58 g / cm³) 3 The following ingredients were added sequentially, and then the mixture was kneaded for 10 seconds. Next, the following admixtures and defoaming agent (AFK-2 (product name) manufactured by Takemoto Oil Co., Ltd.) were added to the kneading water (however, the admixtures and defoaming agent were considered as part of the kneading water), and this kneading water was put into a mixer and kneaded for 180 seconds to obtain a hydraulic composition.

[0084] The following admixtures were used to ensure the mortar flow was within 220 ± 15 mm, and the defoamer was added in an adjusted amount so that the air content of the mixed mortar was 2% or less.

[0085] In Example 1, a strength enhancer X-1, adjusted to a concentration of 40% with deionized water, and a dispersant Y-1 were mixed in a ratio of X-1:Y-1=60:40. This mixture was then diluted with water and used as an admixture.

[0086] Next, Example 2~ 73, reference example 74. Hydraulic compositions for Comparative Examples 1 to 5 were prepared.

[0087] First, using a mechanical mixer specified in JIS R5201, mix ordinary Portland cement (manufactured by Taiheiyo Cement Corporation, density 3.16 g / cm³) according to the formulation (mortar formulation) shown in Table 4. 3 ), blast furnace slag fine powder #4000 (manufactured by Esment Chubu Co., Ltd., density 2.88 g / cm³) 3 ), fine aggregate (Oigawa River system land sand, density 2.58 g / cm³) 3The following ingredients were added sequentially, and then the mixture was kneaded for 10 seconds. Next, the strength enhancers shown in Table 5 (Tables 5-1 to 5-2), the dispersant Y-1, and the defoaming agent (AFK-2 (product name) manufactured by Takemoto Oil Co., Ltd.) were added to the kneading water (however, the strength enhancers, dispersant Y-1, and defoaming agent were considered part of the kneading water), and this kneading water was put into a mixer and kneaded for 180 seconds to obtain a hydraulic composition.

[0088] The strength enhancer was added in an amount ranging from 0.2% to 0.3% relative to the binder (hydraulic binder) when the concentration was set to 100%, as shown in Table 5 (Tables 5-1 to 5-2). The amount of dispersant Y-1 added was adjusted so that the mortar flow was within 220 ± 15 mm. The defoaming agent was added in an amount adjusted so that the air content of the mixed mortar was 2% or less.

[0089] (Mortar flow value) The hydraulic composition immediately after mixing was measured in accordance with JIS R5201, without any free-falling motion.

[0090] (Air volume) The hydraulic composition immediately after mixing was measured using a mortar container in accordance with JIS A1116.

[0091] [Table 4]

[0092] Next, a hardened body was prepared from the obtained hydraulic composition (mortar), and its compressive strength was measured by the following method. The results are shown in Table 5 (Tables 5-1 to 5-2). In Table 5-1, "Blank" means that no strength enhancer was added.

[0093] (Compressive strength of hardened mortar) Six cylindrical tin concrete specimen molds (product name "Summit Mold," manufactured by Sumisho Cement Co., Ltd., with a base diameter of 50 mm and a height of 100 mm) were prepared (two sets of three molds), and mortar was filled into each of them using a two-layer filling method. After that, the specimens were cured in an air-conditioned room at 10°C. Two hours after the mortar was prepared, the surface of the filled mortar was leveled and covered with polyethylene wrap to prevent moisture evaporation. Then, 24 hours and 48 hours after the mortar was prepared, three hardened specimens were removed from the molds, obtaining specimens (hardened mortar) at 24 hours and 48 hours of curing.

[0094] The compressive strength (compressive strength at 24 hours and 48 hours) was measured for each of the obtained specimens at 24 hours and 48 hours of age, and then the average compressive strength of the three specimens was calculated. Furthermore, the compressive strength ratio (%) was calculated based on Comparative Example 1, and evaluation was performed according to the evaluation criteria shown in Table 6. The results are shown in Table 5 (Tables 5-1 to 5-2).

[0095] Furthermore, three specimens (hardened mortar) were prepared using the same method as described above and cured in air at 20°C indoors. Two hours after the preparation of the mortar, the surface of the filled concrete was leveled and covered with polyethylene wrap to prevent moisture evaporation. Then, 24 hours after the preparation of the mortar, the three hardened specimens were removed from the formwork and cured for a further 27 days in water at 20°C. The compressive strength was measured at 28 days of age, and the average compressive strength of the three specimens was calculated. Furthermore, the compressive strength ratio (%) was calculated using Comparative Example 1 as the standard, and the evaluation was performed according to the evaluation criteria shown in Table 6. The results are shown in Table 5 (Tables 5-1 to 5-2).

[0096] [Table 5-1]

[0097] [Table 5-2]

[0098] [Table 6]

[0099] (3) Preparation of hydraulic composition (concrete): Next, the hydraulic compositions of Examples 75 to 94 and Comparative Examples 6 to 9 were prepared as follows.

[0100] First, into a 50 L pan-type forced mixer, with each formulation of β-1 to β-4 shown in Table 8 (concrete formulation), ordinary Portland cement (an equal mixture of those manufactured by Taiheiyo Cement Corporation, Ube-Mitsubishi Cement Corporation, and Sumitomo Osaka Cement Co., Ltd., density 3.16 g / cm 3 ), fine aggregate (Oigawa river system land sand, density 2.58 g / cm 3 ), and coarse aggregate (Okazaki crushed stone, density 2.67 g / cm 3 ) were sequentially charged, and then dry mixed for 10 seconds.

[0101] In the formulations of β-2 to β-4, blast furnace slag fine powder #4000 (manufactured by Esment Chubu Co., Ltd., density 2.88 g / cm 3 ), and fly ash type II (manufactured by Chubu Fly Ash Co., Ltd., density 2.33 g / cm 3 ) were charged simultaneously with the ordinary Portland cement.

[0102] Next, each strength enhancer shown in Table 10, dispersant Y-1, and an antifoaming agent (AFK-2 (trade name) manufactured by Takemoto Yushi Co., Ltd.) were mixed and regarded as a part of the mixing water, and charged together with the mixing water, and then mixed for 120 seconds. In Table 10, "Blank" means that no strength enhancer is added.

[0103] The addition amount of the dispersant Y-1 was set to an amount such that the slump was within 18 ± 1.5 cm. The antifoaming agent was adjusted and added so that the air content of the finished concrete was 2% or less.

[0104] (Slump) The hydraulic composition immediately after mixing was measured in accordance with JIS A1101.

[0105] (Air volume) The hydraulic composition immediately after mixing was measured in accordance with JIS A1128.

[0106] (Preparation of dispersants Y-1 to Y-4) Dispersants Y-1 to Y-4 were prepared as follows, and dispersant Y-1 was used in the preparation of the hydraulic composition (concrete).

[0107] (Dispersant Y-1) First, 140.1 g of deionized water, 168.8 g of α-methacryloyl-ω-methoxy-poly(n=9)oxyethylene, 23.0 g of methacrylic acid, and 1.9 g of 3-mercaptopropionic acid were charged into a 1000 ml round-bottom flask equipped with a stirring blade, stirrer, nitrogen inlet tube, and dropping funnel. After dissolving uniformly while stirring, 9.9 g of 30% sodium hydroxide aqueous solution was slowly added while stirring. After the addition, the atmosphere in the flask was replaced with nitrogen, and the temperature of the reaction system was raised to 60°C in a warm water bath. Next, 63.9 g of 3.0% sodium persulfate aqueous solution was added to the reaction system to start the polymerization reaction. After 2 hours, another 28.8 g of 3.0% sodium persulfate aqueous solution was added to the reaction system and stirred for 2 hours. Subsequently, the reaction mixture was obtained by adjusting the pH to 8 and the concentration to 40% with deionized water and 30% sodium hydroxide aqueous solution. This reaction mixture was designated as dispersant Y-1.

[0108] Furthermore, analysis of the reaction mixture using gel permeation chromatography (GPC) revealed a mass-average molecular weight of 30,000.

[0109] (Dispersant Y-3) In a 1000 ml round-bottom flask equipped with a stirring blade, stirrer, nitrogen inlet tube, and dropping funnel, 76.6 g of deionized water and 147.5 g of α-(3-methyl-3-butenyl)-ω-hydroxy-poly(n=53)oxyethylene were charged and uniformly dissolved while stirring. After that, the atmosphere in the flask was replaced with nitrogen, and the temperature of the reaction system was raised to 65°C in a warm water bath. Then, 27.7 g of 1.0% hydrogen peroxide aqueous solution was added dropwise to the reaction system over 3 hours, followed by 64.1 g of 20% acrylic acid aqueous solution, and then an aqueous solution of 7.0 g of deionized water, 0.8 g of L-ascorbic acid, and 0.6 g of 3-mercaptopropionic acid was added dropwise over 4 hours. These were all added simultaneously. The polymerization reaction was carried out in this manner. After all additions were complete, the temperature was maintained at 65°C for 1 hour, and the polymerization reaction was further carried out. Subsequently, the reaction mixture was prepared by adjusting the pH to 6 and the concentration to 40% using deionized water and a 30% sodium hydroxide aqueous solution to obtain the reaction mixture. This reaction mixture was designated as dispersant Y-3.

[0110] Furthermore, analysis of the reaction mixture using gel permeation chromatography (GPC) revealed a mass-average molecular weight of 40,000.

[0111] (Dispersants Y-2, Y-4) Dispersant Y-2 was prepared in the same manner as dispersant Y-1, except that it contained each constituent unit L and M shown in Table 7 in predetermined proportions while achieving predetermined physical properties. Similarly, Y-4 was prepared in the same manner as dispersant Y-3, except that it contained each constituent unit L and M shown in Table 7 in predetermined proportions while achieving predetermined physical properties.

[0112] [Table 7]

[0113] In Table 7, L-1 to L-4, M-1, and M-2 are as follows: L-1: α-methacryloyl-ω-methoxy-poly(n=9)oxyethylene L-2: α-methacryloyl-ω-methoxy-poly(n=45)oxyethylene L-3: α-(3-methyl-3-butenyl)-ω-hydroxy-poly(n=53)oxyethylene L-4: α-Methallyl-ω-hydroxy-poly(n=113)oxyethylene M-1: Methacrylic acid M-2: Acrylic acid

[0114] (Measurement of mass-average molecular weight) The mass-average molecular weight of the resulting reaction mixture was measured under the following conditions. Equipment: Shodex GPC-101 (manufactured by Showa Denko Corporation) Column: OHpak SB-G + SB-804 HQ + SB-802.5 HQ (manufactured by Showa Denko Corporation) Detector: Differential refractive system (RI) Eluent: 50 mM sodium nitrate aqueous solution Flow rate: 0.7mL / min. Column temperature: 40℃ Sample concentration: 0.5% by mass eluent solution Standard substance: Polyethylene glycol / polyethylene oxide (manufactured by Agilent Technologies, Inc.)

[0115] (Measuring pH) The pH of the resulting reaction mixture was measured under the following conditions. Equipment: pH meter (manufactured by HORIBA) Sample concentration: 1g of sample per 100g of deionized water. Temperature: 20℃

[0116] [Table 8]

[0117] A hardened body was prepared from the obtained hydraulic composition (concrete), and its compressive strength was measured by the following method. The results are shown in Table 10.

[0118] (Compressive strength of hardened concrete) Based on JIS A1132, six cylindrical tinplate concrete specimen molds (product name "Summit Mold," manufactured by Sumisho Cement Co., Ltd., with a base diameter of 100 mm and a height of 200 mm) were prepared (two sets of three molds). Concrete was then filled into each of these molds using a two-layer filling method. After that, the specimens were cured in an air-cured room at 10°C. Two hours after the preparation of the concrete, the surface of the filled concrete was leveled and covered with polyethylene wrap to prevent moisture evaporation. Then, 24 hours and 48 hours after the preparation of the concrete, three hardened specimens were removed from the molds, respectively, to obtain specimens (hardened concrete) at 24 hours and 48 hours of age.

[0119] The compressive strength (compressive strength at 24 hours and 48 hours) was measured for each of the obtained specimens at 24 hours and 48 hours of age, and then the average compressive strength of the three specimens was calculated. Furthermore, the compressive strength ratio (%) was calculated based on Comparative Examples 6 to 9, and the evaluation was performed according to the evaluation criteria shown in Table 9. The results are shown in Table 10.

[0120] Furthermore, three test specimens (hardened concrete) were prepared using the same method as described above and cured in air in a room at 20°C. Two hours after concrete preparation, the surface of the filled concrete was leveled and covered with polyethylene wrap to prevent moisture evaporation. Then, 24 hours after concrete preparation, the three hardened test specimens were removed from the formwork and cured for a further 27 days in water at 20°C. The compressive strength was measured at 28 days of age, and the average compressive strength of the three test specimens was calculated. Furthermore, the compressive strength ratio (%) was calculated based on Comparative Examples 6-9, and evaluated according to the evaluation criteria shown in Table 9. The results are shown in Table 10.

[0121] [Table 9]

[0122] [Table 10]

[0123] (Examples 95-114, Comparative Examples 10-13) (Formulation stability test) To evaluate the formulation stability of the admixture for hydraulic compositions of the present invention, a formulation stability test was conducted under the following conditions.

[0124] Specifically, the strength enhancers shown in Table 11 were diluted with deionized water to a concentration of 40% to prepare a diluted solution of the strength enhancers. Then, this diluted solution of the strength enhancers was mixed with each of the dispersants Y-1 to Y-4 in a mass ratio of 55:45, and the mixture was left to stand for one month at 20°C. The state of the mixture after standing was checked to evaluate the stability of the formulation. The evaluation results are shown in Table 11.

[0125] The evaluation criteria for the formulation stability test were as follows: if the mixture separated into two layers after standing, or if suspended matter or precipitate formed during standing, it was considered "NG"; and if no separation, suspended matter, or precipitate was observed when the mixture was visually inspected after standing, it was considered "OK".

[0126] [Table 11]

[0127] (result) As shown in Tables 5 (Tables 5-1 to 5-2) and 10, it was confirmed that adding the strength enhancer for hydraulic compositions of this embodiment to a hydraulic composition allows for the early development of higher compressive strength during the hardening of the hydraulic composition, and furthermore, that the strength development after a long period of time (compressive strength at 28 days of age) can be maintained. In addition, as shown in Table 11, it was confirmed that the strength enhancer for hydraulic compositions of the present invention has good compatibility with dispersants and exhibits high formulation stability. [Industrial applicability]

[0128] The strength enhancer and admixture for hydraulic compositions of the present invention can be used as additives in hydraulic compositions such as concrete and mortar. Furthermore, the hydraulic compositions of the present invention can be used to form hydraulic composition hardened bodies such as hardened concrete and hardened mortar.

Claims

1. A strength enhancer for hydraulic compositions used in hydraulic compositions containing a hydraulic binder, It contains the following component A and component B, Furthermore, it contains at least one selected from the following components C, D, E, and F. A strength enhancer for hydraulic compositions, characterized in that the mass ratio of component A and component B is A / B = 1.5 / 1 to 5 / 1. Component A: Diethylene glycol. Component B: Glycerin. Component C: a nitrogen-containing organic compound with a molecular weight of 500 or less. Component D: a sulfur-containing organic compound with a molecular weight of 500 or less. Component E: Divalent to tetravalent polyhydric alcohols with a molecular weight of 500 or less (excluding those corresponding to components A, B, C, D, and sugars). The aforementioned component E is, Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,2,4-butanetriol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2- It is at least one selected from the group consisting of cyclopentanediol, 1,3-cyclopentanediol, 1,4-cyclopentanediol, 1,2,5-pentanetriol, triethylene glycol, tetraethylene glycol, pinacol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, dipropylene glycol, tripropylene glycol, trimethylolpropane, and diglycerin. Component F: A carbonate ester compound with a molecular weight of 500 or less.

2. The strength enhancer for hydraulic compositions according to claim 1, comprising at least two selected from component C, component D, component E, and component F.

3. A strength enhancer for a hydraulic composition according to claim 1 or 2, comprising at least three selected from the components C, D, E, and F.

4. If the total content of component A, component B, component C, component D, component E, and component F is 100 parts by mass, A strength enhancer for hydraulic compositions according to any one of claims 1 to 3, comprising 55 to 99 parts by mass of component A and component B in total, and 1 to 45 parts by mass of component C, component D, component E, and component F in total.

5. An admixture for hydraulic compositions, characterized by containing a strength enhancer for hydraulic compositions and a dispersant as described in any one of claims 1 to 4.

6. A hydraulic composition characterized by containing the admixture for hydraulic compositions described in claim 5.

7. A hydraulic composition characterized by containing a strength enhancer for hydraulic compositions according to any one of claims 1 to 4.

8. A cured hydraulic composition, characterized in that it is a cured product of the hydraulic composition described in claim 6 or 7.

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