JP2016124719A - Additive for hydraulic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an additive for hydraulic compositions, which makes excellent the pulverization efficiency of a hydraulic compound when the hydraulic compound is pulverized to produce hydraulic powder, which improves the compressive strength of a hardened body of the hydraulic composition when added to the hydraulic composition, and which makes adequate the bubbling of a water-containing system.SOLUTION: The additive for hydraulic compositions contains the alkanolamine shown by the general formula (1) (in which Ris a hydrogen atom, -CHCHOH, or -CH(CH)CHOH; and Ris -CHCHOH or -CH(CH)CHOH).SELECTED DRAWING: None

Description

  The present invention relates to an additive for a hydraulic composition, a method for producing a hydraulic powder, and a hydraulic composition.

  Various hydraulic powders are produced by pulverizing hydraulic compounds such as Portland cement clinker and blast furnace slag. For example, Portland cement is produced by adding an appropriate amount of gypsum to a clinker obtained by firing raw materials such as limestone, clay, iron slag and the like and then pulverizing them. At that time, in order to increase the grinding efficiency, grinding aids such as diethylene glycol and triethanolamine are used. In the pulverization step, it is desirable that the hydraulic compound is made as efficiently as possible with the desired particle size. For this reason, conventionally, a grinding aid is used in the grinding step. Moreover, it is desirable to obtain a hardened body with higher strength from the hydraulic powder obtained by pulverizing the hydraulic compound.

  For the purpose of providing a mixture cement composition obtained showing a 7-day and 28-day compressive strength curve that meets the minimum standards of Portland cement, US Pat. It is described that a higher trialkanolamine having a hydroxyalkyl group having 3 to 5 carbon atoms is added and used.

  Patent Document 2 discloses that a hydraulic compound such as cement that improves the crushing efficiency of the hydraulic compound and that improves the compressive strength at the time of curing of the resulting hydraulic composition is obtained as a single compound. It is described that an alkanolamine having a freezing point of 0 ° C. or lower is added and used for the purpose of providing a method for producing a hydraulic powder that is compatible with use.

Japanese Patent Laid-Open No. 3-183647 JP 2012-36077 A

In the present invention, when the hydraulic compound is pulverized to produce a hydraulic powder, the pulverization efficiency of the hydraulic compound is good, that is, the time to reach the desired particle size can be shortened, When added to a hydraulic composition, an additive for a hydraulic composition is provided that improves the compressive strength of a cured product of the hydraulic composition and has moderate foaming in a system containing water.
In addition, the present invention provides a hydraulic compound that has good grinding efficiency, that is, can shorten the time to reach a desired particle size, and can improve the compressive strength during curing of the resulting hydraulic composition. A method for producing a hard powder is provided.
Moreover, this invention provides the hydraulic composition which can improve the compressive strength at the time of hardening of the hydraulic composition obtained.

  The present invention relates to an additive for a hydraulic composition containing an alkanolamine represented by the following general formula (1).

[Wherein, R ¹ is a hydrogen atom, —CH ₂ CH ₂ OH, or —CH (CH ₃ ) CH ₂ OH, and R ² is —CH ₂ CH ₂ OH, or —CH (CH ₃ ) CH ₂ OH. ]

  Moreover, this invention relates to the manufacturing method of hydraulic powder which has the process of grind | pulverizing a hydraulic compound in presence of the alkanolamine represented by the said General formula (1).

  The present invention relates to a hydraulic composition containing hydraulic powder, water, and an alkanolamine represented by the general formula (1).

According to the present invention, when a hydraulic compound is pulverized to produce a hydraulic powder, the pulverization efficiency of the hydraulic compound is good, that is, the time to reach a desired particle size can be shortened. When added to a hydraulic composition, there is provided an additive for a hydraulic composition that improves the compressive strength of a cured product of the hydraulic composition and has moderate foaming in a system containing water. The
Further, according to the present invention, the grinding efficiency of the hydraulic compound is good, that is, the time to reach the desired particle size can be shortened, and the compressive strength at the time of curing of the obtained hydraulic composition is improved. A method for producing a hydraulic powder is provided.
Moreover, according to this invention, the hydraulic composition which can improve the compressive strength at the time of hardening of the hydraulic composition obtained is provided.
The present invention is a system in which the specific alkanolamine represented by the general formula (1) can achieve improvement in grinding efficiency of a hydraulic compound and improvement in strength of a cured product of a hydraulic composition, and water. It has been found that foaming is moderate.

There are two reasons why the grindability with the grinding aid is improved. The first reason is to suppress electrostatic aggregation (agglomeration). It is said that when a hydraulic compound such as cement clinker is pulverized, grain boundary fracture and intragranular fracture occur. When the intragranular breakdown occurs, the ionic bond between Ca-O is broken, and a surface in which the cation (Ca ²⁺ ) is excessively present and a surface in which the anion (O ²⁻ ) is excessively present are generated. It is said that the pulverization efficiency deteriorates due to the fact that these are compressed by the impact action of the pulverizer to a distance where electrostatic attraction is exerted and aggregate.

  The second reason is to suppress liquid cross-linking in which the pulverized particles are aggregated through moisture due to moisture in the air, diluting water of the grinding aid, and water generated from the added dihydrate gypsum crystal water. is there. In dry pulverization, pulverized particles cause liquid cross-linking with moisture due to moisture in the air, so that the moisture between the pulverized particles serves as a cushion and the pulverization efficiency deteriorates.

When the alkanolamine according to the present invention is present when the hydraulic compound is pulverized, it can be pulverized to a desired particle size in a short time. Even more action mechanism yet a unknown, the alkanolamines for having chelating ability for Ca ^2+, chelates adsorbed on the fracture surface of the cations (Ca ^2+). As a result, the surface charge on the fracture surface is neutralized and electrostatic agglomeration is suppressed. Furthermore, it is presumed that after adsorption, the hydrophobicity derived from the alkyl structure is imparted to the fracture surface, so that liquid cross-linking due to moisture is suppressed and the grinding efficiency is improved.

On the other hand, in order to improve the compressive strength at the time of hardening of the hydraulic composition, the hydraulic composition is improved by improving the hydration reaction rate of each mineral (C ₃ S, C ₂ S, C ₃ A, C ₄ AF). It is thought that reducing the porosity and further densifying the hydrated product are effective. In particular, in order to improve the long-term compressive strength of 3 days, 7 days or more after water contact, densification of the hydrated product is particularly effective, and among these, it consists of C ₃ A, C ₄ AF and gypsum. It is presumed that promoting the hydration reaction of hydrated products such as ettringite from ettringite to dense monosulfate is effective in improving the long-term compressive strength for 3 days or more after water contact. That is, the alkanolamine of the general formula (1) according to the present invention is different from the mechanism that promotes the removal of the amorphous iron hydroxide gel generated during the hydration of C ₄ AF described in Patent Document 1. The alkanolamine skeleton in which a methyl group is arranged on a carbon atom in the vicinity of the nitrogen atom adjusts the strength of the chelate against calcium ions of gypsum due to steric hindrance, and the amount of chelate increases when the calcium ion concentration is high. When it is low, the chelating ability of calcium ions is thought to be sustained by decreasing the amount of chelate. As a result, it is presumed that gypsum is continuously dissolved and promotes the hydration reaction from ettringite to monosulfate.

<Additive for hydraulic composition>
The additive for hydraulic compositions of the present invention contains an alkanolamine represented by the following general formula (1) (hereinafter sometimes referred to as alkanolamine according to the present invention).

[Wherein, R ¹ is a hydrogen atom, —CH ₂ CH ₂ OH, or —CH (CH ₃ ) CH ₂ OH, and R ² is —CH ₂ CH ₂ OH, or —CH (CH ₃ ) CH ₂ OH. ]

The alkanolamine according to the present invention has a general formula from the viewpoints of improvement in grindability of the hydraulic compound, improvement in compressive strength of the hydraulic composition using the obtained hydraulic powder, and appropriate foaming in the aqueous system. A compound in which R ^{1 in} (1) is a hydrogen atom is preferred.
From the same viewpoint, the alkanolamine according to the present invention is more preferably a compound in which R ¹ in the general formula (1) is a hydrogen atom and R ² is —CH ₂ CH ₂ OH.

  The alkanolamine of the general formula (1) according to the present invention can be obtained by reacting a raw material mono- or dialkanolamine with hydroxyacetone in the presence of hydrogen and a catalyst, removing the catalyst, and purifying by distillation. it can. For example, the manufacturing method described in JP-T-2012-530771 is exemplified.

  The alkanolamine according to the present invention can be used as a salt from the viewpoint of enhancing solubility in water. Salts include mixtures of salts selected from sulfates, acetates, chloride salts, formates, carbonates, silicates, hydroxide salts and mixtures thereof. By improving the water solubility of the alkanolamine according to the present invention, the alkanolamine can be made excellent in handleability. In addition, when using the alkanolamine which concerns on this invention as a salt, mass, such as the usage-amount mentioned later, is not the mass of salt itself, but uses the mass of amine conversion.

The alkanolamine according to the present invention can be used as a hydraulic composition additive in the form of a liquid having a concentration of 100% by mass, but may be used as an aqueous solution from the viewpoint of facilitating handling. When the hydraulic composition additive is an aqueous solution, the content of the alkanolamine according to the present invention is preferably 1% by mass or more, more preferably 10% by mass or more from the viewpoint of shortening the grinding time of the hydraulic compound. 30% by mass or more is more preferable, 35% by mass or more is more preferable, and 40% by mass or more is more preferable.
When used in an aqueous solution, the content of the alkanolamine according to the present invention in the aqueous solution is preferably 99.5% by mass or less, more preferably 99% by mass or less, from the viewpoint of improving handleability such as workability. % By mass or less is more preferable, 70% by mass or less is more preferable, and 60% by mass or less is more preferable.
Summing up these viewpoints, when the additive for hydraulic composition is an aqueous solution, the content of the alkanolamine according to the present invention in the aqueous solution is preferably 1% by mass or more and 99.5% by mass or less, preferably 10% by mass. % To 99% by mass is more preferable, 30% to 90% by mass is more preferable, 40% to 70% by mass is still more preferable, and 40% to 60% by mass is even more preferable.
The hydraulic composition additive is composed of the alkanolamine according to the present invention, or the alkanolamine according to the present invention, preferably 30% by mass to 90% by mass, more preferably 40% by mass to 70% by mass, More preferably, it contains 40% by mass or more and 60% by mass or less and water.

  Examples of the additive for a hydraulic composition of the present invention include an admixture for a hydraulic composition and a grinding aid for a hydraulic compound. Therefore, this invention provides the admixture for hydraulic compositions containing the alkanolamine which concerns on this invention. Moreover, this invention provides the grinding aid of the hydraulic compound containing the alkanolamine which concerns on this invention.

<Method for producing hydraulic powder>
In the method for producing hydraulic powder of the present invention, the hydraulic compound is pulverized in the presence of the alkanolamine according to the present invention to obtain hydraulic powder.
A hydraulic compound is a substance that has the property of curing by reacting with water, and a single substance does not have curability, but when two or more are combined, a hydrate is formed by interaction through water and cured. Refers to a compound. In general, hydraulic compounds include alkaline earth metal oxides and oxides such as SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , TiO ₂ , P ₂ O ₅ , and ZnO hydrate at room temperature or hydrothermal conditions. Form things. Also, as mineral contained in the hydraulic powder, e.g., in _{cement, 3CaO · SiO 2 (C 3} S: _{alite), 2CaO · SiO 2 (C} 2 S: _{belite), 3CaO · Al 2 O 3} ( C ₃ A: calcium aluminate), 4CaO · Al ₂ O ₃ · Fe ₂ O ₃ (C ₄ AF: calcium aluminoferrite), and hydraulic compounds containing these components can be used.

Examples of hydraulic compounds include minerals (C ₃ S, C ₂ S, C ₃ A, C ₄ AF), slag, fly ash, limestone, iron slag, gypsum, alumina, incinerated ash, etc. contained in cement. And can be used as a raw material for hydraulic powders.

When Portland cement is obtained as a hydraulic powder, for example, a clinker (also called a cement clinker, which is a hydraulic compound obtained by firing raw materials such as limestone, clay, iron slag, etc., sometimes contains gypsum. ), A suitable amount of gypsum is added, and finish pulverized to produce a powder having a specific surface area of a brane value of 2500 cm ² / g or more. The brain value is a specific surface area measured by a brain surface area measurement method. The present invention includes a method for producing Portland cement, which includes a step of grinding a clinker in the presence of the alkanolamine according to the present invention.

  The alkanolamine according to the present invention is used as a grinding aid for the hydraulic compound, preferably clinker grinding, and preferably as a grinding aid for finish grinding. The alkanolamine according to the present invention is preferably 0.001 part by mass in terms of solid content with respect to 100 parts by mass of a hydraulic compound as a raw material used for pulverization, for example, from the viewpoint of pulverizing to a desired particle size in a short time. As mentioned above, More preferably, it is 0.003 mass part or more, More preferably, it is 0.005 mass part or more, More preferably, it is 0.01 mass part or more, More preferably, it is 0.015 mass part or more, More preferably, it is 0.00. 02 parts by mass or more, and preferably 0.20 parts by mass or less, more preferably 0.175 parts by mass or less, still more preferably 0.15 parts by mass or less, and even more preferably 0.10 parts by mass or less. Use to make quantity. This amount is based on the total amount of the alkanolamine present in the step of pulverizing the hydraulic compound. Specifically, until the pulverization of the hydraulic compound is completed, the target brane value is reached. It is based on the total amount of the alkanolamine that is present up to now.

  In order to perform pulverization in the presence of the alkanolamine according to the present invention, the alkanolamine according to the present invention is preferably added to a raw material containing a hydraulic compound, for example, a clinker. As a method of adding, there is a method of supplying a liquid product of the alkanolamine according to the present invention or a liquid mixture containing the alkanolamine according to the present invention and other components, preferably in the form of an aqueous solution, by dropping, spraying or the like. Can be mentioned. Examples of other components include an antifoaming agent, water, and known grinding aids other than the alkanolamine according to the present invention. The addition of the alkanolamine to the raw material containing the hydraulic compound or the addition of the alkanolamine and other components may be added all at once, or may be added in portions. . Moreover, you may supply and add continuously or intermittently.

In the method for producing hydraulic powder according to the present invention, the pulverization conditions may be adjusted so that a powder having an appropriate particle size can be obtained depending on the raw material, use, and the like. Generally, the specific surface area, Blaine value is preferably 2500 cm ² / g or more, more preferably 3000 cm ² / g or more, and, preferably 5000 cm ² / g or less, more preferably less than or equal to the powder 4000 cm ² / g It is preferable to grind hydraulic compounds, for example, clinker. The target brain value can be obtained, for example, by adjusting the grinding time. When the pulverization time is lengthened, the brane value tends to increase, and when shortened, the brane value tends to decrease.

  In the present invention, the pulverizing apparatus used for pulverizing the hydraulic compound is not particularly limited, and examples thereof include a ball mill which is widely used for pulverizing cement and the like. The material of the grinding media (grinding balls) of the apparatus is preferably one having a hardness equal to or higher than that of the material to be ground (for example, calcium aluminate in the case of cement clinker). Steel, stainless steel, alumina, zirconia, titania, tungsten carbide and the like can be mentioned.

  In the hydraulic powder obtained by the production method of the present invention, the alkanolamine according to the present invention is preferably 0.0005% by mass or more, more preferably from the viewpoint of improving the grindability of the hydraulic compound. 0.001% by mass or more, more preferably 0.003% by mass, even more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, still more preferably 0.015% by mass or more, more More preferably, it is 0.02 mass% or more, and is 0.20 mass% or less, More preferably, it is 0.175 mass% or less, More preferably, it is 0.15 mass% or less, More preferably, it is 0.10 mass%. Contains the following.

  The alkanolamine according to the present invention is used as a grinding aid for grinding hydraulic compounds, has good grinding efficiency, and can improve the compressive strength during curing of the hydraulic composition.

  The alkanolamine according to the present invention is suitable as a grinding aid for hydraulic compounds, especially for clinker. That is, when a hydraulic compound is pulverized, a hydraulic compound pulverization method using the alkanolamine according to the present invention as a pulverization aid is provided. In that case, from the viewpoint of shortening the pulverization time, the alkanolamine according to the present invention is preferably 0.001 part by mass or more and 0.20 part by mass or less, more preferably 0 with respect to 100 parts by mass of the hydraulic compound. 0.003 to 0.175 parts by mass, more preferably 0.005 to 0.15 parts by mass, and even more preferably 0.01 to 0.10 parts by mass. Used for. Among them, from the viewpoint of shortening the pulverization time, the alkanolamine according to the present invention is preferably 0.001 part by mass or more and 0.20 part by mass or less, more preferably 0.003 part by mass with respect to 100 parts by mass of the clinker. To 0.175 parts by mass, more preferably 0.005 to 0.15 parts by mass, and even more preferably 0.01 to 0.10 parts by mass.

  When using the aqueous solution of the alkanolamine according to the present invention, the content of the alkanolamine according to the present invention is preferably 1% by mass or more, preferably 10% by mass or more in the aqueous solution, from the viewpoint of shortening the grinding time of the hydraulic compound. Is more preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, and from the viewpoint of improving handling properties such as workability, it is 99.5% in an aqueous solution. % By mass or less is preferable, 99% by mass or less is more preferable, 90% by mass or less is more preferable, 70% by mass or less is more preferable, and 60% by mass or less is more preferable. From the viewpoint of shortening the grinding time of the hydraulic compound, the amount of the aqueous solution is preferably 0.20 parts by mass or less, more preferably 0.15 parts by mass or less, and 0.10 parts by mass with respect to 100 parts by mass of the hydraulic compound. Part or less is more preferable, and 0.08 part by weight or less is still more preferable. Further, from the viewpoint of workability such as weighing and adding operation when using the hydraulic compound for grinding, the amount of water in the aqueous solution is 0.0001 mass relative to 100 parts by mass of the hydraulic compound. Part or more, preferably 0.001 part by weight or more, more preferably 0.20 part by weight or less, more preferably 0.10 part by weight or less, and 0.08 part by weight or less. Is more preferably 0.07 parts by mass or less, and still more preferably 0.05 parts by mass or less. This amount of water is based on the total amount of the aqueous solution used in the step of pulverizing the hydraulic compound. Specifically, until the pulverization of the hydraulic compound is completed, the target brane value is reached. This is based on the total amount of aqueous solution used.

  The alkanolamine according to the present invention may be used in combination of two or more, but preferably one is used. In the present invention, the single compound is excellent in improving the grinding efficiency of the hydraulic compound and the compression strength at the time of hardening of the hydraulic composition. In order to cope with various grinding conditions, the alkanol according to the present invention is further provided. It can be used in combination with known grinding aids other than amines. For example, known grinding aids such as diethylene glycol and monoacetin, other alkanolamines (such as triethanolamine and diethanolamine), glycerin that is a natural component from the viewpoint of safety, ethylene oxide adduct of glycerin, propylene oxide adduct of glycerin, etc. May be blended.

  The hydraulic composition using the hydraulic powder obtained by the production method of the present invention has improved compressive strength at the time of curing. Examples of the hydraulic powder include Portland cement, blast furnace slag, alumina cement, fly ash, limestone, and gypsum.

  The hydraulic powder obtained by the production method of the present invention can be used as a material for concrete structures and concrete products. The concrete using the hydraulic powder obtained by the production method of the present invention has improved compressive strength after 3 days, which is an indicator of demolding from water contact, and after 28 days, which is an indicator of the final strength of the cured body. Therefore, for example, even if the hydraulic powder obtained by the manufacturing method of the present invention is blended and replaced with a hydraulic powder (blast furnace slag, fly ash, limestone, etc.) having a low initial age strength after water contact. Compared with the case where the hydraulic powder in which the present invention is not used is used, the compression strength after 3 days and 28 days after water contact can be obtained.

<Hydraulic composition>
The hydraulic composition of the present invention contains hydraulic powder, water, and the alkanolamine according to the present invention.

  The hydraulic powder used in the hydraulic composition of the present invention is a powder having physical properties that are cured by a hydration reaction, and cement, gypsum, and the like are preferable. Preferred are ordinary Portland cement, Belite cement, medium heat cement, early strong cement, super early strong cement, sulfate resistant cement, etc., and blast furnace slag, fly ash, silica fume, stone powder (calcium carbonate powder), etc. Blast furnace slag cement, fly ash cement, silica fume cement or the like to which is added may be used. In addition, the hydraulic composition finally obtained by adding sand, sand and gravel as aggregates to these powders is generally called mortar, concrete, etc., respectively. The hydraulic powder produced by the production method of the present invention can be used as the hydraulic powder.

  From the viewpoint of promoting the hydration reaction, the hydraulic composition of the present invention is preferably 0.001 part by mass or more, more preferably 0.001 part by mass or more, based on 100 parts by mass of the hydraulic powder. 005 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 2 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.1 parts by mass or less.

  The hydraulic composition of the present invention preferably contains an aggregate. The aggregate includes an aggregate selected from fine aggregate and coarse aggregate. Examples of the fine aggregate include those defined in JIS A0203-2302. Fine aggregates include river sand, land sand, mountain sand, sea sand, lime sand, silica sand and crushed sand, blast furnace slag fine aggregate, ferronickel slag fine aggregate, lightweight fine aggregate (artificial and natural) and reclaimed Examples include fine aggregates. Moreover, what is prescribed | regulated by JIS A0203-2303 is mentioned as a coarse aggregate. Examples of coarse aggregates include river gravel, land gravel, mountain gravel, sea gravel, lime gravel, crushed stones, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural) and recycled Coarse aggregate etc. are mentioned. Different types of fine aggregates and coarse aggregates may be used in combination, or a single type may be used.

The aggregate content in the hydraulic composition of the present invention is preferably 1700 kg / m ³ or more per volume of the hydraulic composition from the viewpoint of separation resistance and workability of the hydraulic composition, and is 1720 kg / m ^3. or more, and then, preferably 1800 kg / ^{m 3} or less, 1760kg / ^{m 3} or less is more preferable.

  The volume ratio [s / a × 100 (%)] of the fine aggregate (s) in the aggregate (a) in the hydraulic composition of the present invention is the viewpoint of separation resistance and workability of the hydraulic composition. Therefore, 45% or more is preferable, 47% or more is more preferable, 55% or less is preferable, and 53% or less is more preferable.

The hydraulic composition of the present invention can contain a dispersant from the viewpoint of increasing fluidity. Dispersants such as phosphate ester polymers, polycarboxylic acid copolymers, sulfonic acid copolymers, naphthalene polymers, melamine polymers, phenol polymers, lignin polymers, etc. Is mentioned. The dispersant may be an admixture containing other components.
When a dispersant is used, the hydraulic composition of the present invention is preferably 0.1 parts by mass or more, more preferably 0.15 parts by mass of the dispersant (as an effective component) with respect to 100 parts by mass of the hydraulic powder. Part or more, more preferably 0.2 part by weight or more, and preferably 2 parts by weight or less, more preferably 1.8 parts by weight or less, still more preferably 1.6 parts by weight or less.

  The hydraulic composition of the present invention has a water / hydraulic powder ratio [mass percentage (mass%) of water and hydraulic powder in the slurry, usually abbreviated as W / P. , W / C may be abbreviated. Is preferably 60% by mass or less, more preferably 58% by mass or less, still more preferably 57% by mass or less, still more preferably 56% by mass or less, still more preferably 55% by mass or less, and preferably 15 mass% or more, More preferably, it is 18 mass% or more, More preferably, it is 20 mass% or more, More preferably, it is 23 mass% or more.

  In the present invention, the pulverization aid maintains low foaming properties, but an antifoaming agent can be used in combination from the viewpoint of suppressing strength reduction due to an increase in the amount of air in the hydraulic composition.

  As the antifoaming agent, a silicone-based antifoaming agent, a fatty acid ester-based antifoaming agent, and an ether-based antifoaming agent are preferable. In the silicone-based antifoaming agent, dimethylpolysiloxane is more preferable, and in the fatty acid ester-based antifoaming agent, polyalkylene glycol. Fatty acid esters are more preferred, and polyalkylene glycol ethers are more preferred for ether-based antifoaming agents.

  The hydraulic composition of the present invention is used in the field of ready-mixed concrete, concrete vibration products, self-leveling, refractory, plaster, gypsum slurry, lightweight or heavy concrete, AE, repair, pre-packed, tray It is useful in any field of various concrete such as for grouting, for ground improvement, for cold weather.

The following are mentioned as a manufacturing method of the hydraulic composition of this invention.
Step (1) of obtaining hydraulic powder by the method for producing hydraulic powder of the present invention,
A step (2) of mixing the hydraulic powder obtained in the step (1) with water to obtain a hydraulic composition;
The manufacturing method of the hydraulic composition which has this.
In this production method, the matters described in the hydraulic composition additive of the present invention, the production method of the hydraulic powder, and the hydraulic composition can be appropriately applied.

<Synthesis method>
The alkanolamines A1, A2 and A3 according to the present invention used in the examples were synthesized by the following method.

[Synthesis Method of A1]
1741.0 g of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added to a 3 liter glass four-necked flask, and then monoethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) and hydroxyacetone (Wako Pure Chemical Industries, Ltd. ( Co., Ltd.) were prepared, and stirred for several minutes until a uniform solution was obtained. Thereafter, 0.95 g of platinum oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was charged, and the solution was stirred for 8 hours at a stirring speed of 400 rpm while keeping the solution at 30 ° C. while bubbling hydrogen at a flow rate of 180.0 mL / min. Reacted. After completion of the reaction, filtration was performed with a PTFE material membrane filter (pore system 0.2 μm), and then methanol was removed from the reaction solution using an evaporator. The resulting solution was distilled while raising the temperature under 0.10 kPa, thereby obtaining a fraction 1 separated at a boiling point of 100 to 109 ° C and a fraction 2 separated at a boiling point of 110 to 120 ° C. The boiling point is a value obtained by measuring the vapor temperature of the product before entering the cooling pipe. As a result of gas chromatography (GC) analysis and NMR analysis, it was found that fraction 2 was the target alkanolamine of A1. From the GC analysis, the yield of A1 alkanolamine was 79% and the purity was 97% or more. The alkanolamine of A1 was a compound in which R ¹ in the general formula (1) was a hydrogen atom and R ² was —CH ₂ CH ₂ OH.

[Method for synthesizing A2]
1558.0 g of methanol was added to a 3 liter glass four-necked flask, and then 2-amino-1-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and hydroxyacetone were respectively added to 141.0 g and 182.0 g, and a uniform solution Stir for a few minutes until Thereafter, 0.96 g of platinum oxide was charged, and hydrogen was bubbled at a flow rate of 180.0 mL / min, and the solution was stirred and reacted for 8 hours at a stirring speed of 400 rpm while maintaining the solution at 30 ° C. The subsequent operations up to distillation are the same as in the synthesis method of A1. Then, the obtained solution was distilled while raising the temperature under 0.10 kPa to obtain a fraction 1 separated at a boiling point of 100 to 109 ° C. and a fraction 2 separated at a boiling point of 110 to 120 ° C. As a result of gas chromatography (GC) analysis and NMR analysis, it was found that fraction 2 was the target alkanolamine of A2. From the GC analysis, the yield of alkanolamine of A2 was 87%, and the purity was 98% or more. The alkanolamine of A2 was a compound in which R ¹ in the general formula (1) was a hydrogen atom and R ² was —CH (CH ₃ ) CH ₂ OH.

[Method for synthesizing A3]
1253.0 g of 1,2-dichloroethane was added to a 3 liter glass four-necked flask, and then 33.6 g and 23.7 g of diethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) and hydroxyacetone were charged, respectively. Stir until 2.5 hours. Thereafter, 19.2 g and 95.4 g of acetic acid and sodium triacetoxyborohydride (manufactured by Wako Pure Chemical Industries, Ltd.) were added, respectively, and the solution was maintained at 30 ° C. in a nitrogen atmosphere at a stirring speed of 400 rpm. The reaction was stirred for 0 hour. Thereafter, neutralization was performed using an aqueous sodium hydroxide solution having a concentration of 1 mol / L to complete the reaction. The obtained aqueous solution was transferred to a separatory funnel, to which 714.0 g of diethyl ether was added, and the reaction product was extracted into a diethyl ether layer. This operation was performed twice. Next, an appropriate amount of magnesium sulfate was added to the resulting diethyl ether solution for dehydration. Then, it filtered with the membrane filter (pore system 0.2 micrometer) of the PTFE raw material, and isolate | separated diethyl ether using the evaporator then. The resulting solution was distilled while raising the temperature under 0.10 kPa, fraction 1 separated at a boiling point of 100 to 109 ° C, fraction 2 separated at a boiling point of 110 to 119 ° C, and separated at a boiling point of 120 to 130 ° C. Fraction 3 was obtained. As a result of gas chromatography (GC) analysis and NMR analysis, it was found that fraction 3 contained the most alkanolamine of the target A3. According to the GC analysis for fraction 3, the yield of alkanolamine of A3 was 6.4%, and the purity was 98% or more. Therefore, distillation purification was performed to adjust the yield of alkanolamine of A3. The alkanolamine of A3 was a compound in which R ¹ in the general formula (1) was —CH ₂ CH ₂ OH and R ² was —CH ₂ CH ₂ OH.

<Evaluation test>
An evaluation in the case of using an alkanolamine of A1 to A3 and a comparative alkanolamine as a grinding aid and an evaluation in the case of an aqueous solution were performed.
The following materials are used in the following blending amounts, charged in a lump and pulverized by a ball mill (crushing time to reach the target brain value), and hardening of the hydraulic composition using the resulting cement The compression strength test at the time and the foaming property test were evaluated as follows. The results are shown in Table 1.

(1-1) Materials Used / Clinker: Components are CaO: about 65%, SiO ₂ : about 22%, Al ₂ O ₃ : about 5%, Fe ₂ O ₃ : about 3%, MgO and others: about 3% Clinker for ordinary Portland cement obtained by primary pulverization using a crusher and a grinder with a combination of limestone, clay, silica, iron oxide raw materials, etc. (mass basis) object).
Dihydrate gypsum: Gypsum with an amount of SO ₃ of 45.93% by mass. Additive: See Table 1.

(1-2) Compounding amount / clinker: 1000 g
・ Dihydrate gypsum: 37.0 g (1.7 parts by mass of SO _{3 with} respect to 100 parts by mass of clinker)
-Powder auxiliary agent: The compound of Table 1 was used by 50 mass% aqueous solution so that the addition amount with respect to 100 mass parts of hydraulic compounds (clinker) might become as Table 1. FIG.

(1-3) Ball mill AXB-15 manufactured by Seiwa Giken Co., Ltd., stainless steel pot capacity of 18 liters (outer diameter 300 mm), stainless steel balls 30 mmφ (nominal 1/4), 20 mmφ (nominal 3 / 4), a total of 100 70 pieces, and the rotation speed of the ball mill was set to 35 rpm. A part of the pulverized material was discharged during sampling and sampled.

(1-4) a milling arrival time target Blaine value and 3300 ± 100cm ² / g, 60 minutes from the start grinding, 75 minutes, measure the Blaine values for the sample after 90 minutes, reaches the target Blaine value 3300 cm ² / g The time was determined by a quadratic regression equation of Microsoft Excel 2003 manufactured by Microsoft Corporation. The pulverization was completed with this time as the final arrival time (crush arrival time). For the measurement of the brane value, a brane air permeation device defined in the physical test method for cement (JISR 5201) was used. The difference in the crushed arrival time in this test becomes a larger difference at the actual machine level. The shorter the pulverization time, the better the pulverizability. The pulverization arrival time is a value with Comparative Example 4 as 100. The pulverization arrival time of Comparative Example 4 was 145 minutes.

(1-5) Compressive strength test Cement physical test method (JISR 5201) annex 2 (cement test method-measurement of strength) with a brane value of 3300 ± 100 cm ² / g obtained in the pulverization time test Measured according to Higher compressive strength is desirable from the viewpoint of manufacturing concrete products and structures. The relative value of the compressive strength is a value with Comparative Example 4 as 100.

(1-6) Foamability test Foam that contacts the wall surface of the sample bottle after 10% by mass of the alkanolamine in Table 1 is placed in the sample bottle, shaken by hand for 30 seconds, and left standing. The foaming other than was visually confirmed and classified into the following five evaluation criteria. If it is 4 or less by evaluation criteria, it is within the range of foaming acceptable as a product.
-Evaluation criteria 1: All bubbles disappear within 30 seconds after standing.
2: After standing, all the bubbles disappear within 60 seconds exceeding 30 seconds.
3: After standing, all bubbles disappear within 60 seconds over 60 seconds.
4: After standing, all bubbles disappear within 120 seconds over 120 seconds.
5: Bubbles remain after 180 seconds after standing.

Claims (7)

The additive for hydraulic compositions containing the alkanolamine represented by following General formula (1).

[Wherein, R ¹ is a hydrogen atom, —CH ₂ CH ₂ OH, or —CH (CH ₃ ) CH ₂ OH, and R ² is —CH ₂ CH ₂ OH, or —CH (CH ₃ ) CH ₂ OH. ] The additive for hydraulic compositions according to claim 1, wherein the alkanolamine is a compound in which R ¹ in the general formula (1) is a hydrogen atom. The manufacturing method of hydraulic powder which has the process of grind | pulverizing a hydraulic compound in presence of the alkanolamine represented by following General formula (1).

[Wherein, R ¹ is a hydrogen atom, —CH ₂ CH ₂ OH, or —CH (CH ₃ ) CH ₂ OH, and R ² is —CH ₂ CH ₂ OH, or —CH (CH ₃ ) CH ₂ OH. ] It said alkanolamine is R ¹ in the general formula (1) is a compound of hydrogen atoms, claim 3 manufacturing method of hydraulic powder according.   The manufacturing method of the hydraulic powder of Claim 3 or 4 whose abundance of the said alkanolamine is 0.001 mass part or more and 0.20 mass part or less with respect to 100 mass parts of hydraulic compounds. A hydraulic composition containing hydraulic powder, water, and an alkanolamine represented by the following general formula (1).

[Wherein, R ¹ is a hydrogen atom, —CH ₂ CH ₂ OH, or —CH (CH ₃ ) CH ₂ OH, and R ² is —CH ₂ CH ₂ OH, or —CH (CH ₃ ) CH ₂ OH. ]   The hydraulic composition of Claim 6 which contains 0.001 mass part or more and 2 mass parts or less of alkanolamine represented by General formula (1) with respect to 100 mass parts of hydraulic powder.