WO2014148522A1

WO2014148522A1 - Method for producing hydraulic powder

Info

Publication number: WO2014148522A1
Application number: PCT/JP2014/057453
Authority: WO
Inventors: 下田政朗; 佐川桂一郎; 長澤浩司; 中村圭介
Original assignee: 花王株式会社
Priority date: 2013-03-22
Filing date: 2014-03-19
Publication date: 2014-09-25
Also published as: BR112015021743A2; JP2014185049A; JP6039476B2; CN105026334B; MX2015013453A; CN105026334A

Abstract

The present invention is a method for producing hydraulic powder having a step for pulverizing a hydraulic compound in the presence of glycerin and hydroxymethanesulfonic acid or a salt thereof.

Description

Method for producing hydraulic powder

The present invention relates to a method for producing hydraulic powder, which includes a step of pulverizing a hydraulic compound.
Background art

The initial strength of the hydraulic composition, for example, the initial strength of the concrete, is important for determining the initial properties of the concrete, such as the form sliding speed, frost damage resistance, and the timing of removing the siding plate in the slip foam method. For example, the retention period of the formwork is stipulated in JASS 5 and Ministry of Construction Notification No. 110, but the minimum retention period is 2 to 3 days (foundation, pillars, walls, etc.) at an air temperature of 15 ° C or higher. Yes. The reason is that the expression of long-term strength due to drying of the concrete after demolding is remarkably deteriorated, and it is said that the evaporation of water within 3 days is particularly remarkable. In order to suppress this, it is effective to promote the hydration reaction of the cement and convert it into a cement hydrate that is hard to dry (evaporate). This is important from the viewpoint of suppressing long-term strength reduction due to drying of the cured product.

On the other hand, in the cement industry, waste (general garbage, etc.) and by-products generated in other industries have been actively used as raw materials, energy sources, and parts of products. However, the cement strength may vary greatly. Cement quality standards are classified into strength classes (3 ranks of 28-day strength and 2 ranks of initial strength) from the viewpoint of strength, as in Europe and China. However, the 3-day strength expressed by the initial strength is dependent on the initial hydration reaction of the cement, and the mineral composition is likely to change due to wastes. For this reason, it is important from the viewpoint of stable production of cement to make the initial strength high. In addition, blast furnace slag and fly ash, which are by-products of other industries, are used as a mixture for cement products, but expressing a high initial strength increases the amount of mixing within the range of quality standards. It becomes possible to reduce the amount of clinker. Reducing the amount of clinker is important from the viewpoint of reducing the emission of greenhouse gases generated during clinker production.

In JP 2008-542182, a grinding aid composition comprising at least one biomass-derived polyol selected from diols, triols, or mixtures thereof is introduced into particles for the production of powders such as cement. There is disclosed a method for improving the pulverization efficiency of particles comprising:

On the other hand, JP-A-6-199555 discloses that a hardening accelerator component for shortening the setting time of a cement composition containing a hydraulic cement binder; and the hardening acceleration of the hardening accelerator component are increased. An admixture comprising a C2 to C6 glycol component present in an effective amount is disclosed.

Japanese Patent Laid-Open No. Sho 61-117142 discloses a cement composition containing sodium hydroxymethanesulfonate and sodium thiocyanate as a cement composition with accelerated curing.

Further, EP-A 1731491 corresponds to US-A 2008/0308013, and discloses a cement composition containing calcium nitrite and a formic acid compound to accelerate the setting time.
Summary of invention

The present invention relates to a method for producing hydraulic powder, comprising a step of pulverizing a hydraulic compound in the presence of glycerin and hydroxymethanesulfonic acid or a salt thereof.

Moreover, this invention contains glycerol and hydroxymethanesulfonic acid or its salt, and mass ratio (glycerol / hydroxymethanesulfonic acid or its salt) of glycerol and hydroxymethanesulfonic acid or its salt is 5/95 or more. , 55/45 or less, the additive composition for grinding hydraulic compounds.
Furthermore, the present invention provides the above-mentioned additive composition for pulverizing a hydraulic compound in a total amount of glycerol and hydroxymethanesulfonic acid or a salt thereof, 0.001 part by mass or more, The present invention relates to a method for improving the strength of a cured body of a hydraulic powder, which is present in an amount of 100 parts by mass or less and pulverizes a hydraulic compound to obtain a hydraulic powder.
Furthermore, the present invention relates to the use of the additive composition for grinding a hydraulic compound as an additive during grinding of the hydraulic compound.
Furthermore, the present invention relates to the use of the additive composition for grinding a hydraulic compound for improving the strength of a cured product of a hydraulic powder obtained by grinding a hydraulic compound.
Detailed Description of the Invention

Due to reasons such as improving the productivity of hydraulic powder, improving the productivity of secondary concrete products, and improving the strength of the hardened concrete, the hydraulic powder manufacturing method uses the pulverizability of hydraulic compounds and the resulting hydraulic properties. Further improvement is desired in both the compressive strength, especially the initial strength, at the time of curing of the hydraulic composition using the powder.

The present invention provides a method for producing a hydraulic powder from which a cured product having a high initial strength can be obtained without inhibiting the grindability of the hydraulic compound.

According to the present invention, there is provided a method for producing a hydraulic powder from which a cured product having a high initial strength can be obtained without inhibiting the grindability of the hydraulic compound. According to the present invention, the above additive composition is added when the hydraulic compound is pulverized.

The method for producing a hydraulic powder according to the present invention is characterized in that a hydraulic compound is pulverized in the presence of glycerin and hydroxymethanesulfonic acid or a salt thereof, without impairing the pulverizability of the hydraulic compound. The effect of improving the compressive strength at the time of hardening of the hydraulic composition obtained, especially an initial stage strength is produced. The reason for such an effect is not clear, but is considered as follows.

In the present invention, the presence of glycerin and hydroxymethanesulfonic acid or a salt thereof at the time of pulverization of the hydraulic compound does not inhibit the pulverization effect of glycerin, and the hydraulic property generated by the pulverization in the same manner as glycerin. By covering the powder surface, aggregation of the hydraulic powder is suppressed, so that it is presumed that the grindability is not inhibited.

When a hydraulic composition is prepared from the pulverized hydraulic powder, the hydroxymethanesulfonic acid of the present invention is made of C ₃ S (alite), which is one component of the hydraulic powder mineral, by an appropriate chelating action. It is presumed that the crystals are atomized by acting on the crystal growth of a hydrated product such as calcium hydroxide. Glycerin is also presumed to promote ion elution of C ₃ A (calcium aluminate) and C ₄ AF (calcium aluminoferrite), which are mineral components of hydraulic powder, by an appropriate chelating action. Furthermore, when a mixed material (such as blast furnace slag and fly ash) is contained, it is estimated that hydroxymethanesulfonic acid promotes ion elution of the mixed material. In the present invention, by coexistence of hydroxymethanesulfonic acid and glycerin, C ₃ S, mixed material, and respective eluted ions from C ₃ A and C ₄ AF are complexed, and a hydrated product having a porous crystal structure is obtained. Therefore, it is presumed that the ingress of water to the surface of the hydraulic powder is maintained and the hydration reaction proceeds continuously without being inhibited, so that the compressive strength after 3 days from water contact is improved. Furthermore, by making these both exist at the time of pulverization, they exist in the vicinity of the surface of the hydraulic powder, effectively promote the hydration reaction for each mineral and mixed material, and very little for the hydraulic compound. It is presumed that the effect of improving the hydration rate, and thus the effect of improving the initial strength of the cured product, is exhibited even with the added amount.

Commercially available products can be used for glycerin. As glycerin, commercially available refined glycerin, for example, glycerin obtained by transesterification of oil derived from palm can be used. From the viewpoint of shortening the time required to reach the required strength of the hydraulic composition, purified glycerin is preferable.

The amount of glycerin is preferably 0.0005 parts by mass or more, more preferably 0.001 with respect to 100 parts by weight of the hydraulic compound as the raw material used for pulverization, from the viewpoint of pulverizability and initial strength of the hydraulic compound. Part by mass, more preferably 0.003 parts by mass or more, still more preferably 0.005 parts by mass or more, still more preferably 0.010 parts by mass or more, and from the viewpoint of the additive cost during pulverization, Preferably it is 0.040 mass parts or less, More preferably, it is 0.035 mass parts or less, More preferably, it is 0.020 mass parts or less, More preferably, it is 0.016 mass parts or less.

A commercially available product can be used as hydroxymethanesulfonic acid or a salt thereof. Examples of the salt include alkali metal salts, alkaline earth metal salts, and ammonium salts, and alkali metal salts are preferable from the viewpoint of shortening the time required to reach the required strength of the hydraulic composition. Examples of the alkali metal salt include sodium salt and potassium salt, and examples of the alkaline earth metal salt include calcium salt, and sodium salt is preferable from the viewpoint of availability.

The amount of hydroxymethanesulfonic acid or a salt thereof is preferably 0.0005 parts by mass or more from the viewpoint of the grindability and initial strength of the hydraulic compound with respect to 100 parts by weight of the hydraulic compound as a raw material used for grinding. More preferably 0.001 parts by mass or more, still more preferably 0.005 parts by mass or more, still more preferably 0.010 parts by mass or more, still more preferably 0.020 parts by mass or more, and addition during pulverization From the viewpoint of agent cost, it is preferably 0.060 parts by mass or less, more preferably 0.050 parts by mass or less, still more preferably 0.030 parts by mass or less, and still more preferably 0.024 parts by mass or less.

The total abundance of glycerin and hydroxymethanesulfonic acid or a salt thereof is preferably 0.001 part by mass or more and 0.100 part by mass or less with respect to 100 parts by weight of the hydraulic compound as a raw material used for pulverization. This abundance is preferably 0.001 parts by mass or more, more preferably 0.004 parts by mass or more, still more preferably 0.010 parts by mass or more, and still more preferably, from the viewpoints of grindability and initial strength of the hydraulic compound. Is 0.020 parts by mass or more, more preferably 0.030 parts by mass or more, and from the viewpoint of the additive cost during pulverization, it is preferably 0.100 parts by mass or less, more preferably 0.085 parts by mass. Hereinafter, it is more preferably 0.050 part by mass or less, and still more preferably 0.040 part by mass or less.

This amount is based on the total amount of glycerin and hydroxymethanesulfonic acid or salt thereof present in the step of grinding the hydraulic compound, specifically, until the grinding of the hydraulic compound is complete. Is based on the total amount of glycerin and hydroxymethanesulfonic acid or salt thereof present until reaching the target brane value as described below.

Further, the mass ratio of glycerin to hydroxymethanesulfonic acid or a salt thereof (glycerin / hydroxymethanesulfonic acid or a salt thereof) is preferably 5/95 or more and 55/45 or less. This mass ratio is more preferably 10/90 or more, still more preferably 15/85 or more, still more preferably 25/75 or more, and still more preferably 35/65, from the viewpoint of grindability and initial strength of the hydraulic compound. More preferably, it is 50/50 or less, and further preferably 45/55 or less from the viewpoint of the initial strength.

In order to perform pulverization in the presence of glycerin and hydroxymethanesulfonic acid or a salt thereof, it is preferable to add glycerin and hydroxymethanesulfonic acid or a salt thereof to a raw material containing a hydraulic compound such as clinker. As a method of adding, a method of supplying a liquid material containing glycerin and hydroxymethanesulfonic acid or a salt thereof, preferably an aqueous solution, by dropping, spraying or the like can be mentioned. Each of glycerin and hydroxymethanesulfonic acid or a salt thereof may be separately added to the hydraulic compound as a liquid, preferably an aqueous solution, or may be added to the hydraulic compound after mixing both. Examples of other components include an antifoaming agent and water. Addition of glycerin and hydroxymethanesulfonic acid or its salt or addition of glycerin and hydroxymethanesulfonic acid or its salt and other ingredients to the raw material containing hydraulic compound is done by adding all the final amount used at once. Alternatively, it may be added in divided portions. Moreover, you may add continuously or intermittently.

In the method for producing hydraulic powder of the present invention, a hydraulic compound is pulverized to obtain hydraulic powder. A hydraulic compound is a substance that cures by reacting with water, such as clinker, and is not curable alone, such as fly ash or blast furnace slag, but it reacts with water or an alkaline substance. When combined with a substance having the property of being cured, it refers to both substances that form a hydrate by interaction through water and cure. Examples of the substance having the property of being cured by reacting with water include oxides of alkaline earth metals, oxides such as SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , TiO ₂ , P ₂ O ₅ , and ZnO. It is done. These generally form hydrates at room temperature or hydrothermal conditions. For example, in a clinker, 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) is contained. In addition, when combined with a substance that has a property of curing by reacting with water or an alkaline substance by itself, a substance that forms a hydrate by interaction through water and cures, for example, Those having a pozzolanic action (fly ash, silica fume, volcanic ash, silicic acid white clay) and those having latent hydraulic properties (blast furnace slag) can be mentioned. In the present invention, a substance that does not have curing properties by itself but has a property of curing by reacting with water or an alkaline substance is combined with a substance that forms a hydrate by interaction through water and cures. It is defined as “material”. The mixed material is preferably at least one selected from fly ash, blast furnace slag and silica fume, and more preferably at least one selected from fly ash and blast furnace slag.

The hydraulic compound preferably contains a substance capable of curing by reacting with water or an alkaline substance, and further, a substance capable of curing by reacting with water, particularly clinker, blast furnace slag, fly ash. And one or more mixed materials selected from the group consisting of silica fume (hereinafter referred to as the mixed material (a)) are preferred. The content of the mixed material (a) is preferably 8% by mass or more, more preferably 25% by mass or more, and further preferably 40% by mass in the hydraulic compound from the viewpoint of the strength improvement rate from no addition at 3 days strength. % Or more, and preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less. The remainder of this content is preferably a substance having the property of reacting with water and curing. Therefore, the hydraulic compound containing the mixed material (a) has a content of a substance having a property of curing by reacting with water such as clinker in the hydraulic compound, preferably 20% by mass or more, more preferably It is 30% by mass or more, more preferably 40% by mass or more, and preferably 92% by mass or less, more preferably 75% by mass or less, and still more preferably 60% by mass or less. The total content of the mixed material (a) and the substance having the property of reacting with water or an alkaline substance such as clinker and the mixed material (a) is preferably 70% by mass or more, more preferably 90%. The content is preferably not less than mass% and not more than 100 mass%, and may be 100 mass%. The production method of the present invention is suitable as a production method of mixed cement (for example, JIS R 5211 to 5213).

When obtaining Portland cement as hydraulic powder, for example, Portland cement is a clinker (also called cement clinker, which is a hydraulic compound obtained by firing raw materials such as limestone, clay, iron slag, etc., and contains gypsum. May be pre-ground, added with an appropriate amount of gypsum, finish-ground, and a specific surface area of a predetermined specific surface area, for example, a brain value of 2500 cm ² / g or more, or a BET specific surface area of 0.8 m ² / g or more. It is manufactured as a powder having Similarly, a hydraulic powder containing a mixed material can be produced using both the clinker and the mixed material.

In the method for producing a hydraulic powder of 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, application (cement strength class), and the like. Generally, when a hydraulic compound is a substance alone having a property of curing a water react with as cement clinker, Blaine value is preferably 2500 cm ² / g or more, more preferably 3000 cm ² / g or more, and preferably It is preferable to grind the hydraulic compound until it becomes 5000 cm ² / g or less, more preferably 4000 cm ² / g or less. In addition, when the hydraulic compound contains a material such as a cement clinker that cures by reacting with water and a mixed material, the density (specific gravity) of the hydraulic compound is unknown and it becomes difficult to measure the brane value. Sometimes. In this case, a BET specific surface area can be substituted. The BET specific surface area is a gas adsorption method in which gas particles such as nitrogen (N ₂ ) are adsorbed on solid particles and the surface area is measured from the adsorbed amount. Specifically, the specific surface area is obtained by measuring the monomolecular adsorption amount VM by the BET equation (Brunauer, Emmet and Teller's equation) from the relationship between the pressure P and the adsorption amount V. When pulverizing a hydraulic compound containing a substance that can be cured by reaction with water, such as a cement clinker, preferably a substance having a property that can be cured by reacting with water, such as a cement clinker, and a mixture When the contained hydraulic compound is pulverized, the BET specific surface area is preferably 0.8 m ² / g or more, more preferably 1.2 m ² / g or more, and preferably 3.0 m ² / g or less, more preferably It is preferable to grind the hydraulic compound until the powder becomes a powder of 2.5 m ² / g or less. The target specific surface area can be obtained by adjusting the pulverization time, for example, in either case of Blaine value or BET specific surface area. If the pulverization time is lengthened, the specific surface area tends to be large, and if it is shortened, the specific surface area tends to be small.

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). , Stainless steel, alumina, zirconia, titania, tungsten carbide and the like.

From the viewpoint of suppressing strength reduction due to an increase in the amount of air in the hydraulic composition, an antifoaming agent can be used in combination. Moreover, by making an antifoamer exist at the time of the grinding | pulverization of a hydraulic compound, an antifoamer can be uniformly distributed on the surface of the hydraulic powder obtained, and the said inhibitory effect can also be expressed more effectively. That is, until the desired particle size is reached by the method for producing hydraulic powder, comprising the step of pulverizing the hydraulic compound in the presence of glycerin, hydroxymethanesulfonic acid or a salt thereof and an antifoaming agent. Time can be shortened. That is, the pulverization efficiency is good, and a decrease in the compressive strength of the hydraulic composition due to an increase in the air amount can be suppressed.

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 using the hydraulic powder obtained by the production method of the present invention has improved compressive strength during curing, especially initial strength. Examples of the hydraulic powder include Portland cement (JIS R 5210), blast furnace cement (JIS R 5211), silica cement (JIS R 5212), fly ash cement (JIS R 5213), and alumina cement. A mixed cement mixed at a certain ratio is preferred.

The hydraulic powder obtained by the production method of the present invention can be used for a hydraulic composition such as concrete. The hydraulic powder obtained by the production method of the present invention can be used, for example, as a material for a concrete structure or a concrete product. Since the concrete using the hydraulic powder obtained by the production method of the present invention has improved initial compressive strength such as 3 days after water contact, for example, to the hydraulic powder obtained by the production method of the present invention, Compared to the case of using a hydraulic powder not yet implemented in the present invention, even if hydraulic powder with low initial age strength after contact with water (blast furnace slag, fly ash, silica fume, limestone, etc.) is blended and replaced. Thus, it has an advantage that the compressive strength after 3 days from water contact can be obtained, which is equal or better.

Further, from the viewpoint of improving the workability at the time of grinding the hydraulic compound, it contains glycerin and hydroxymethanesulfonic acid or a salt thereof, and the mass ratio of glycerin to hydroxymethanesulfonic acid or a salt thereof (glycerin / hydroxymethanesulfone). An additive composition for grinding a hydraulic compound having an acid or a salt thereof of 5/95 or more and 55/45 or less can be used as an additive at the time of grinding the hydraulic compound. In the strength improver composition for hydraulic powder, the mass ratio of glycerin to hydroxymethanesulfonic acid or a salt thereof (glycerin / hydroxymethanesulfonic acid or a salt thereof) is preferably in the above-mentioned range. Moreover, the hydraulic powder obtained by grind | pulverizing the hydraulic compound of the additive composition for grinding | pulverizing a hydraulic compound can be used for the strength improvement of the hardening body of this hydraulic powder. In addition, the hardened | cured material of hydraulic powder is a hardened | cured material of the hydraulic composition prepared with the material containing hydraulic powder and water.

The strength improver composition for hydraulic powder is preferably a liquid composition from the viewpoint of improving workability such as addition operation. In order for the form of the strength improver composition for hydraulic powder to be a liquid composition, a solvent can be contained. As the solvent, water is preferable. The content of the solvent is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass. It is at most 70% by mass, more preferably at most 70% by mass, even more preferably at most 60% by mass. Moreover, the strength improver composition for hydraulic powder may contain other additives such as an antifoaming agent.

The total amount of glycerin and hydroxymethanesulfonic acid or a salt thereof in the strength improver composition for hydraulic powder is preferably 5% by mass or more, more preferably from the viewpoint of improving the 3-day strength of the hydraulic composition. 10% by weight or more, more preferably 20% by weight or more, still more preferably 30% by weight or more, still more preferably 40% by weight or more, and from the viewpoint of workability such as addition operation, preferably 80% by weight or less, More preferably, it is 70 mass% or less, More preferably, it is 60 mass% or less.

The strength improver composition for hydraulic powder according to the present invention is prepared so that, when the hydraulic compound is pulverized, the amount of glycerin and hydroxymethanesulfonic acid or a salt thereof and the total amount thereof are the above-mentioned abundance. It is preferable to add to the hard composition.

Embodiments of the present invention are exemplified below.
<1> A method for producing hydraulic powder, comprising a step of pulverizing a hydraulic compound in the presence of glycerin and hydroxymethanesulfonic acid or a salt thereof.

<2> The amount of glycerin is preferably 0.0005 parts by mass or more, more preferably 0.001 parts by mass or more, still more preferably 0.003 parts by mass or more, and still more preferably 100 parts by weight of the hydraulic compound. Preferably it is 0.005 mass part or more, More preferably, it is 0.010 mass part or more, Preferably it is 0.040 mass part or less, More preferably, it is 0.035 mass part or less, More preferably, it is 0.020 mass. The method for producing a hydraulic powder according to <1>, wherein the amount is 0.01 part by mass or less, more preferably 0.016 part by mass or less.

<3> The abundance of hydroxymethanesulfonic acid or a salt thereof is preferably 0.0005 parts by mass or more, more preferably 0.001 parts by mass or more, and still more preferably 0.005 with respect to 100 parts by weight of the hydraulic compound. Parts by mass or more, more preferably 0.010 parts by mass or more, still more preferably 0.020 parts by mass or more, and preferably 0.060 parts by mass or less, more preferably 0.050 parts by mass or less, further Preferably, it is 0.030 mass part or less, More preferably, it is 0.024 mass part or less, The manufacturing method of the hydraulic powder as described in said <1> or <2>.

<4> The total abundance of glycerin and hydroxymethanesulfonic acid or a salt thereof is preferably 0.001 part by mass or more, more preferably 0.004 part by mass or more, further preferably 100 parts by weight of the hydraulic compound. Is 0.010 parts by mass or more, more preferably 0.020 parts by mass or more, still more preferably 0.030 parts by mass or more, and 0.100 parts by mass or less, more preferably 0.085 parts by mass or less. The method for producing a hydraulic powder according to any one of <1> to <3>, further preferably 0.050 part by mass or less, and further preferably 0.040 part by mass or less.

<5> The mass ratio of glycerin to hydroxymethanesulfonic acid or a salt thereof (glycerin / hydroxymethanesulfonic acid or a salt thereof) is preferably 5/95 or more, more preferably 10/90 or more, and even more preferably 15/85 or more. More preferably, it is 25/75 or more, more preferably 35/65 or more, and 55/45 or less, preferably 50/50 or less, more preferably 45/55 or less, <1> to <4> The method for producing a hydraulic powder according to any one of the above.

<6> The hydraulic compound contains a substance having a property of curing by reacting with water, and one or more mixed materials selected from the group consisting of blast furnace slag, fly ash and silica fume,
The content of the substance having the property of curing by reacting with water is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and preferably 92% in the hydraulic compound. % By mass or less, more preferably 75% by mass or less, still more preferably 60% by mass or less,
The content of the mixed material in the hydraulic compound is preferably 8% by mass or more, more preferably 25% by mass or more, still more preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass. % Or less, more preferably 60% by mass or less,
The method for producing hydraulic powder according to any one of <1> to <5>.

<7> The total content of the substance having a property of reacting with water and curing and the mixed material is preferably 70% by mass or more, more preferably 90% by mass or more, and 100% by mass or less in the hydraulic compound. The method for producing hydraulic powder according to <6>, further comprising 100% by mass.

<8> Hydraulic compound, react with water to contain a substance mixed material having the property of curing, BET specific surface area is preferably 0.8 m ² / g or more, more preferably 1.2 m ² / The hydraulic compound is pulverized until it becomes a powder of g or more and preferably 3.0 m ² / g or less, more preferably 2.5 m ² / g or less, according to the above <6> or <7> A method for producing hydraulic powder.

<9> The above-mentioned <1> to <8>, wherein the grinding device used for grinding is a ball mill, and the material of the grinding balls is one or more selected from steel, stainless steel, alumina, zirconia, titania, tungsten carbide. The manufacturing method of the hydraulic powder in any one of.

<10> Contains glycerin and hydroxymethanesulfonic acid or a salt thereof, and the mass ratio of glycerin to hydroxymethanesulfonic acid or a salt thereof (glycerin / hydroxymethanesulfonic acid or a salt thereof) is 5/95 or more, 55 / An additive composition for crushing hydraulic compounds, which is 45 or less.

<11> The additive composition for grinding a hydraulic compound according to <10>, wherein the form is a liquid composition.

<12> A solvent, preferably water is contained, and the content of the solvent is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and preferably 95% by mass or less. More preferably 90% by mass or less, still more preferably 80% by mass or less, still more preferably 70% by mass or less, and still more preferably 60% by mass or less, The additive for pulverizing a hydraulic compound according to the above <11> Composition.

<13> The total amount of glycerin and hydroxymethanesulfonic acid or a salt thereof in the strength improver composition for hydraulic powder is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass. Or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, <10 > An additive composition for grinding a hydraulic compound according to any one of <12>.

<14> A method for improving the strength of a cured body of a hydraulic powder, wherein the additive composition for pulverizing the hydraulic compound is added to pulverize the hydraulic compound to obtain a hydraulic powder.

<15> The additive composition for pulverizing the hydraulic compound is a total of glycerol and hydroxymethanesulfonic acid or a salt thereof, and is 0.001 part by mass or more and 0.100 part by mass with respect to 100 parts by mass of the hydraulic compound. The strength improvement method of the hardening body of the hydraulic powder which makes it exist below and pulverizes a hydraulic compound and obtains hydraulic powder.

<16> The hydraulic powder according to <14> or <15>, wherein the abundance of glycerin is 0.0005 parts by mass or more and 0.040 parts by mass or less with respect to 100 parts by weight of the hydraulic compound. To improve the strength of the cured product.

<17> Any of <14> to <16>, wherein the amount of hydroxymethanesulfonic acid or a salt thereof is 0.0005 parts by mass or more and 0.060 parts by mass or less with respect to 100 parts by weight of the hydraulic compound. A method for improving the strength of a cured product of a hydraulic powder according to claim 1.

<18> The hydraulic compound contains a substance having a property of being cured by reacting with water, and one or more mixed materials selected from the group consisting of blast furnace slag, fly ash, and silica fume, and reacts with the water. The content of the substance having the property of being cured is 20% by mass or more and 92% by mass or less in the hydraulic compound, and the content of the mixed material is 8% by mass or more and 80% by mass in the hydraulic compound. The method for improving the strength of a cured body of a hydraulic powder according to any one of <14> to <17>, wherein:

<19> The <14> to <18> above, wherein the hydraulic compound is pulverized until the BET specific surface area of the hydraulic compound becomes a powder having a BET specific surface area of 0.8 m ² / g or more and 3.0 m ² / g or less. The strength improvement method of the hardening body of the hydraulic powder in any one of.

<20> Use of the additive composition for grinding a hydraulic compound as an additive at the time of grinding a hydraulic compound.

<21> Use for improving the strength of a cured product of a hydraulic powder obtained by pulverizing a hydraulic compound of the additive composition for pulverizing the hydraulic compound.
Examples The following examples describe the practice of the present invention. The examples are illustrative of the invention and are not intended to limit the invention.

(1) Hydraulic compound The following hydraulic compound in which clinker, dihydrate gypsum, and a mixed material were mixed and different in the mixed material content was used.
A hydraulic compound having a mixed material content of 0% by mass: 95% by mass of clinker and 5% by mass of dihydrate gypsum were mixed.
A hydraulic compound having a mixed material content of 5% by mass: 90% by mass of clinker, 5% by mass of dihydrate gypsum, and 5% by mass of granulated blast furnace slag were mixed.
-Hydraulic compound with mixed material content of 10% by mass: 86% by mass of clinker, 4% by mass of dihydrate gypsum, 5% by mass of granulated blast furnace slag, and 5% by mass of fly ash were mixed.
-Hydraulic compound with mixed material content of 30% by mass: 67% by mass of clinker, 3% by mass of dihydrate gypsum, 15% by mass of granulated blast furnace slag, and 15% by mass of fly ash were mixed.
A hydraulic compound having a mixed material content of 47% by mass: 50% by mass of clinker, 3% by mass of dihydrate gypsum, 25% by mass of granulated blast furnace slag, and 22% by mass of fly ash were mixed.
A hydraulic compound having a mixed material content of 70% by mass: 28% by mass of clinker, 2% by mass of dihydrate gypsum, 35% by mass of granulated blast furnace slag, and 35% by mass of fly ash were mixed.

Clinker and dihydrate gypsum are blast furnace granulated slag and fly ash are as follows.
Clinker: The 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% (mass basis) Ordinary Portland cement clinker (3.5mm sieve passing material) obtained by primary pulverization of limestone, clay, silica, iron oxide raw materials, etc.
・ Dihydrate gypsum: Reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd. ・ Blast furnace granulated slag: Blast furnace granulated slag obtained by primary crushing with a crusher and grinder (3.5 mm sieve passing material), "Slag".
Fly ash: Commercially available product, manufactured by Chubu Electric Power Co., Inc., indicated as “FA” in the table.

(2) Preparation of additive composition for grinding hydraulic compound Glycerin and sodium hydroxymethanesulfonate were mixed at the mixing ratios shown in Tables 1 to 5, and the solid content concentration (effective component concentration) was adjusted to a 50% by mass aqueous solution. The concentration was adjusted by adding water. None of the pulverizing additive compositions was turbid, and a uniform aqueous solution was obtained. In addition, glycerin and sodium hydroxymethanesulfonate are as follows.
・ Glycerin: 1,2,3-propanetriol manufactured by Wako Pure Chemical Industries, Ltd. ・ Sodium hydroxymethanesulfonate: manufactured by Tokyo Chemical Industry Co., Ltd.

(3) Measurement of BET specific surface area of hydraulic powder The BET specific surface area was measured using Macsorb HM-model 1201 (manufactured by Mountaintech) under the following conditions.
Degassing: 100 ° C. × 30 minutes, cooling × 4 minutes Measurement gas: Helium was used as a carrier gas, and nitrogen was used as a coolant and adsorbate. Further, the mixed gas concentration was 30.4%, and the flow rate was 25 ml / min. It was.

(4) Preparation of hydraulic composition and compressive strength test A hydraulic composition was prepared according to the physical test method of cement (JIS R 5201), Annex 2 (Test method of cement-measurement of strength). The compressive strength of the obtained hydraulic composition was evaluated in accordance with Cement Physical Test Method (JIS R 5201), Annex 2 (Cement Test Method—Measurement of Strength).

<Example 1 and Comparative Example 1>
The additive shown in Table 1 is added to 600 g of a hydraulic compound having a mixed material content of 47% by mass in the form shown in Table 1 in the form of an additive composition for grinding, and in the presence of the additive, a ball mill is added. The powder was pulverized with a hydraulic powder.

The ball mill uses AXB-15 manufactured by Seiwa Giken Co., Ltd., the capacity of the stainless steel pot is 18 liters (outer diameter 300mm), and the stainless steel balls are 70mm, 30mmφ (Nominal 1/3/16), 20mmφ (Nominal 3/4) A total of 175 balls including 70 balls and 35 30 mmφ alumina balls were used, and the rotation speed of the ball mill was 45 rpm. Further, the BET specific surface area after pulverization for 38 minutes was measured.

Using the hydraulic powder obtained after pulverization for 38 minutes, the compressive strength after 3 days and 28 days after the preparation of the hydraulic composition was measured. The results are shown in Table 1.

In Comparative Example 1-1, neither glycerin nor sodium hydroxymethanesulfonate was added during the production of the hydraulic powder (during pulverization), and Comparative Example 1-2 had a predetermined amount shown in the table after pulverization. The additive was added to the kneading water at the time of preparing the mortar in the form of an additive composition for grinding. In Comparative Example 1-3, only glycerin was added in the form of an aqueous solution during the production of the hydraulic powder (during pulverization), and Comparative Example 1-4 was produced during the production of the hydraulic powder (during pulverization). ), Only sodium hydroxymethanesulfonate was added in the form of a 50% by weight aqueous solution. In Comparative Examples 1-5 and 1-6, sodium bisulfite or calcium nitrate, which is a curing accelerator component described in JP-A-6-199555, is used instead of sodium hydroxymethanesulfonate. It was used during grinding in the form of a grinding additive composition.

* Relative value with the result of Comparative Example 1-1 as 100

In Table 1, as shown in Comparative Example 1-2, even when glycerin and sodium hydroxymethanesulfonate are added to the hydraulic powder as an additive after pulverization, the 3-day strength is not significantly improved. On the other hand, in Example 1-1, both glycerin and sodium hydroxymethanesulfonate are present at the time of pulverization of the hydraulic compound, so that the pulverization is good with a small amount of addition, and the curing is excellent in strength for 3 days. It turns out that the hydraulic powder from which a body is obtained can be manufactured. Therefore, the difference of the effect by the addition time of glycerin and sodium hydroxymethanesulfonate is clear.

<Example 2 and Comparative Example 2>
In Example 1-1, the same procedure as in Example 1-1 was performed, except that the total amount of glycerin and sodium hydroxymethanesulfonate was 0.080 parts by mass with respect to 100 parts by mass of the hydraulic compound. The experiment was conducted. Similarly to Comparative Example 1-2, Comparative Example 2-1 and Comparative Example 2-2 also add the predetermined amount of additives shown in the table after pulverization to the kneading water used in the preparation of the mortar in the form of an additive composition for pulverization. did. The results are shown in Table 2.

* Relative value with the result of Comparative Example 1-1 as 100

From the results of Table 2, as in Example 2-1, both glycerin and sodium hydroxymethanesulfonate are present when the hydraulic compound is pulverized, so that the pulverizability is improved with a small amount of addition, and It turns out that the hydraulic powder from which the hardening body excellent in the intensity | strength for 3 days is obtained can be manufactured.

<Examples 3 to 7 and Comparative Examples 3 to 7>
In Example 1-1, an experiment was performed in the same manner as in Example 1-1 except that hydraulic compounds having different mixed material contents were used. Similarly, the comparative example was added to the kneading water at the time of preparing the mortar in the form of an additive composition for pulverization after pulverization. The results are shown in Table 3. Table 3 also shows the results of Example 1-1 and Comparative Examples 1-1 and 1-2.

* Relative value with the result of each comparative example with a branch number of "-1" being 100

From Table 3, as the ratio of the mixed material in the hydraulic compound increases, the three-day strength tends to decrease, but in the examples according to the method of the present invention, the hydraulic compound containing the mixed material at any ratio It can be seen that a hydraulic powder can be produced from which a hardened body with good grindability and excellent initial strength can be obtained.

<Example 8>
In Example 1-1, the experiment was performed in the same manner as in Example 1-1 except that the mass ratio of glycerin and sodium hydroxymethanesulfonate was changed. The results are shown in Table 4. Table 4 also shows the results of Example 1-1 and Comparative Example 1-1.

* Relative value with the result of Comparative Example 1-1 as 100

Table 4 shows that the mass ratio of glycerin to hydroxymethanesulfonic acid or a salt thereof (glycerin / hydroxymethanesulfonic acid or a salt thereof) has a more suitable range.

<Example 9>
In Example 1-1, an experiment was performed in the same manner as in Example 1-1 except that the total amount of glycerin and sodium hydroxymethanesulfonate was changed. The results are shown in Table 5. Table 5 also shows the results of Example 1-1 and Comparative Example 1-1.

* Relative value with the result of Comparative Example 1-1 as 100

Table 5 shows that the total abundance of glycerin and hydroxymethanesulfonic acid or its salt has a more suitable range. In particular, when the total abundance of glycerin and hydroxymethanesulfonic acid or a salt thereof is 0.02 parts by mass or more with respect to 100 parts by weight of the hydraulic compound as a raw material, the grindability and initial strength may be further improved. Recognize.

Claims

A method for producing hydraulic powder, comprising a step of pulverizing a hydraulic compound in the presence of glycerin and hydroxymethanesulfonic acid or a salt thereof.
The total abundance of the glycerin and the hydroxymethanesulfonic acid or a salt thereof is 0.001 part by mass or more and 0.100 part by mass or less with respect to 100 parts by mass of the hydraulic compound. A method for producing hydraulic powder.
The hydraulic powder according to claim 1 or 2, wherein a mass ratio of the glycerin to the hydroxymethanesulfonic acid or a salt thereof (glycerin / hydroxymethanesulfonic acid or a salt thereof) is 5/95 or more and 55/45 or less. Body manufacturing method.
The method for producing hydraulic powder according to any one of claims 1 to 3, wherein the amount of glycerin is 0.0005 parts by mass or more and 0.040 parts by mass or less with respect to 100 parts by weight of the hydraulic compound. .
The water according to any one of claims 1 to 4, wherein the presence amount of hydroxymethanesulfonic acid or a salt thereof is 0.0005 parts by mass or more and 0.060 parts by mass or less with respect to 100 parts by weight of the hydraulic compound. Manufacturing method of hard powder.
The hydraulic compound contains a substance having a property of being cured by reacting with water and one or more mixed materials selected from the group consisting of blast furnace slag, fly ash and silica fume, and is cured by reacting with the water. The content of the substance having properties is 20% by mass or more and 92% by mass or less in the hydraulic compound, and the content of the mixed material is 8% by mass or more and 80% by mass or less in the hydraulic compound. The method for producing hydraulic powder according to any one of claims 1 to 5.
The hydraulic compound is pulverized until the BET specific surface area of the hydraulic compound becomes a powder having a BET specific surface area of 0.8 m 2 / g or more and 3.0 m 2 / g or less. A method for producing hydraulic powder.
It contains glycerin and hydroxymethanesulfonic acid or a salt thereof, and the mass ratio of glycerin to hydroxymethanesulfonic acid or a salt thereof (glycerin / hydroxymethanesulfonic acid or a salt thereof) is 5/95 or more and 55/45 or less. An additive composition for grinding a hydraulic compound.
The additive composition for grinding a hydraulic compound according to claim 8 is a total of glycerol and hydroxymethanesulfonic acid or a salt thereof, and is 0.001 part by mass or more and 0.000 part by mass with respect to 100 parts by mass of the hydraulic compound. A method for improving the strength of a cured body of a hydraulic powder, which is present in an amount of 100 parts by mass or less to obtain a hydraulic powder by pulverizing a hydraulic compound.
The method for improving the strength of a cured body of a hydraulic powder according to claim 9, wherein the abundance of glycerin is 0.0005 parts by mass or more and 0.040 parts by mass or less with respect to 100 parts by weight of the hydraulic compound.
11. The hydraulic powder according to claim 9, wherein the amount of hydroxymethanesulfonic acid or a salt thereof is 0.0005 parts by mass or more and 0.060 parts by mass or less with respect to 100 parts by weight of the hydraulic compound. A method for improving the strength of a cured product.
The hydraulic compound contains a substance having a property of being cured by reacting with water and one or more mixed materials selected from the group consisting of blast furnace slag, fly ash and silica fume, and is cured by reacting with the water. The content of the substance having properties is 20% by mass or more and 92% by mass or less in the hydraulic compound, and the content of the mixed material is 8% by mass or more and 80% by mass or less in the hydraulic compound. The method for improving the strength of a cured body of a hydraulic powder according to any one of claims 9 to 11.
The hydraulic compound is pulverized until the BET specific surface area of the hydraulic compound becomes a powder of 0.8 m 2 / g or more and 3.0 m 2 / g or less. A method for improving the strength of a cured body of hydraulic powder.
Use of the additive composition for grinding a hydraulic compound according to claim 8 as an additive during grinding of the hydraulic compound.
Use of the additive composition for grinding a hydraulic compound according to claim 8 for improving the strength of a cured product of a hydraulic powder obtained by grinding a hydraulic compound.