JP2006160577A - Hydraulic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide good performance such as no bleeding, excellent fluid retention, excellent dimensional stability after curing even when the ratio of slag fine aggregate in the fine aggregate is increased. A hydraulic composition suitable as a composition is provided.
SOLUTION: A cationic surfactant [compound (A)], one or more compounds selected from the group consisting of an anionic aromatic compound and a bromide compound [compound (B)], water, and hydraulic properties A hydraulic composition containing powder and slag fine aggregate, wherein the aqueous solution of the compound (A) and the aqueous solution of the compound (B) exhibit a specific viscosity behavior.
[Selection figure] None

Description

  The present invention relates to a hydraulic composition such as a composition for a self-leveling material used for preparing a floor base material of a general building.

  Blast furnace slag fine aggregate is a kind of slag aggregate that is produced as a by-product when metal is extracted from ore during refining, and is used in hydraulic compositions from the viewpoint of aggregate resource problems and effective utilization of resources. Consideration has been made.

  Patent Document 1 discloses a grout material containing slag fine aggregate. Patent Document 2 discloses a concrete containing slag fine aggregate and limestone crushed sand. Patent Document 3 discloses blast furnace slag fine aggregate-containing concrete using a specific dispersant for blast furnace slag fine aggregate. Patent Document 4 discloses a self-leveling composition containing a large amount of inorganic powder.

On the other hand, in Patent Document 5, from the viewpoint of modifying the rheology of the slurry, two specific types of hydraulic compositions with a high weight ratio of water to hydraulic powder of 0.5 to 30 are used. It has been proposed to use a water-soluble low-molecular compound in combination.
JP-A-7-309658 JP 2000-302499 A JP 2001-322853 A JP 2002-47051 A JP 2004-91217 A

  If you can use a large amount of slag fine aggregate, which is industrial waste, while maintaining the properties required for self-leveling materials such as excellent fluidity retention, excellent breathing suppression, excellent dimensional stability after curing, etc. This is desirable in the industry as it enables the development of new aggregate resources. However, slag fine aggregate is considered to be unsuitable for use as a fine aggregate of self-leveling material among hydraulic compositions, and studies for blending it in large quantities have not been made sufficiently in the past. .

  Even when a large amount of slag fine aggregate is used, the present invention is required for a hydraulic composition, particularly a self-leveling material, excellent in fluid retention, excellent in breathing suppression, and excellent in dimensional stability after curing. It is an object of the present invention to provide a hydraulic composition capable of maintaining the characteristics such as the above.

The present invention relates to a cationic surfactant (hereinafter referred to as compound (A)) and one or more compounds selected from the group consisting of an anionic aromatic compound and bromide compound (hereinafter referred to as compound (B)). A hydraulic composition containing water, hydraulic powder, and slag fine aggregate,
The combination of the compound (A) and the compound (B) is an aqueous solution S _A of the compound (A) (having a viscosity at 20 ° C. of 100 mPa · s or less) and an aqueous solution S _B of the compound (B) (viscosity at 20 ° C. Is a combination in which the viscosity at 20 ° C. of an aqueous solution mixed with a 50/50 weight ratio is at least twice as high as the viscosity of any aqueous solution (20 ° C.) before mixing. It relates to a hard composition. The present invention also relates to a cured product obtained by curing the hydraulic composition of the present invention.

  The present invention also provides a hydraulic composition having a step of mixing the specific compound (A) and the specific compound (B) according to the present invention with water, hydraulic powder, and slag fine aggregate. It relates to a manufacturing method.

  According to the present invention, even when a large amount of slag fine bone is used, it is possible to maintain required characteristics such as long pot life, suppression of breathing, and excellent dimensional stability after curing. A hydraulic composition suitable as a composition can be provided.

  As mentioned above, conventionally, examination which applies a slag fine aggregate to a self-leveling material use was not fully made | formed. Self-leveling materials are used for building floor surfaces, and are required to diffuse and diffuse large areas such as building floors without excessive vibration and to harden the surface smoothly and quickly. The Therefore, the composition for SL material requires high fluidity and fast curing, and conventionally, in order to ensure fluidity without increasing the water-cement ratio (W / C), the SL material composition is more than fine aggregate. In general, a large amount of fine inorganic powder is contained (Patent Document 4).

  On the other hand, slag fine aggregate has almost no fine particles and has a square particle size. Therefore, a large amount of water is required to secure fluidity, and breathing easily occurs due to material separation. In addition, the actual volume ratio, which is a physical property important for fluidity, is not stipulated in JIS, and quality tends to vary depending on the production location, production lot, etc., and stable fluidity is difficult to obtain.

  Therefore, the slag fine aggregate is not suitable for the use of a self-leveling material, and development to the use of a self-leveling material has not been sufficiently studied. Patent Documents 1 to 3 and Patent Document 5 do not disclose the use of slag fine aggregates for self-leveling materials.

  The present inventors made up for the shortcomings of the slag fine aggregate as a self-leveling material, and, as a result of detailed investigations for imparting good properties as a self-leveling material, the specific compound (A) and the compound ( In combination with B), it has been found that a self-leveling material containing a large amount of slag fine aggregate can be obtained, and the present invention has been completed.

  In the compound (A) and compound (B) according to the present invention, in a single aqueous solution of the compound (A) or compound (B), a single molecule or a structure such as an aggregate, micelle, or liquid crystal is formed in water. In addition, the viscosity of the aqueous solution is low in the mixed state, and the viscosity of the mixed solution can be greatly increased by mixing the aqueous solution of the compound (A) and the aqueous solution of the compound (B). Therefore, it is a requirement that the compound (A) and the compound (B) used in the present invention have a specific viscosity expression when the compound (A) and the compound (B) are combined. (B) cannot be specified individually, but can be specified only by “expressing the above requirements by mixing the compound (A) and the compound (B)”.

<Compound (A)>
Among the compounds (A), a quaternary salt type cationic surfactant is preferable as a compound selected from cationic surfactants, and the quaternary salt type cationic surfactant includes 10 to 26 in the structure. Those having at least one saturated or unsaturated linear or branched alkyl group containing 1 carbon atom are preferred. For example, alkyl (10 to 26 carbon atoms) trimethylammonium salt, alkyl (10 to 26 carbon atoms) pyridinium salt, alkyl (10 to 26 carbon atoms) imidazolinium salt, alkyl (10 to 26 carbon atoms) dimethylbenzylammonium salt Specifically, hexadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium methosulfate, octadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, tallow trimethyl ammonium chloride, tallow trimethyl ammonium bromide, hydrogen Tallow trimethylammonium chloride, hydrogenated tallow trimethylammonium bromide, hexadecylethyldi Examples include tillammonium chloride, octadecylethyldimethylammonium chloride, hexadecylpropyldimethylammonium chloride, hexadecylpyridinium chloride, 1,1-dimethyl-2-hexadecylimidazolinium chloride, hexadecyldimethylbenzylammonium chloride, and the like. Two or more kinds may be used in combination. Specifically, from the viewpoint of water solubility and thickening effect, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, hexadecylpyridinium chloride and the like are preferable. Further, from the viewpoint of thickening performance, two or more cationic surfactants having different alkyl chain lengths may be used in combination.

<Compound (B)>
Among the compounds (B), those selected from anionic aromatic compounds include carboxylic acids having an aromatic ring and salts thereof, phosphonic acids and salts thereof, sulfonic acids and salts thereof, specifically, salicylic acid, p-toluenesulfonic acid, sulfosalicylic acid, benzoic acid, m-sulfobenzoic acid, p-sulfobenzoic acid, 4-sulfophthalic acid, 5-sulfoisophthalic acid, p-phenolsulfonic acid, m-xylene-4-sulfonic acid, Cumene sulfonic acid, methyl salicylic acid, styrene sulfonic acid, chlorobenzoic acid, and the like. These may form a salt, and two or more of these may be used in combination. However, in the case of a polymer, the weight average molecular weight (for example, gel permeation chromatography method / polyethylene oxide conversion) is preferably less than 500.

  Of the compounds (B), those selected from bromide compounds are preferably inorganic salts such as sodium bromide, potassium bromide, and hydrogen bromide.

<Slag fine aggregate>
As slag aggregates defined in JIS A 5011, (1) blast furnace slag aggregate, (2) ferronickel slag aggregate, (3) copper slag aggregate, (4) electric furnace oxidation slag aggregate, (5 ) Molten slag aggregate. Although these can be used in the present invention, blast furnace slag aggregate is particularly useful. In general, slag fine aggregates having an average particle diameter of about 0.5 to 3 mm are known among these slag aggregates, and they can also be used in the present invention. In addition, a slag fine aggregate having a density (JIS A 5011) of 2.5 g / cm ³ or more can be used.

<Hydraulic composition>
In the hydraulic composition of the present invention, particularly the self-leveling material composition, the total effective content of the compound (A) and the compound (B) is 0.01 to 20 parts by weight with respect to 100 parts by weight of water, The range of 0.1 to 15 parts by weight, particularly 0.3 to 10 parts by weight is preferable in terms of suppressing the separation of materials such as breathing water.

  Moreover, in the hydraulic composition of the present invention, particularly the composition for a self-leveling material, the molar ratio (effective molar ratio) of the compound (A) to the compound (B) is the ratio of the compound (A) to the compound (B). The region where the thickening effect is high differs depending on the combination, and may be appropriately determined according to the target degree of thickening. From the viewpoint of the obtained viscosity and the shape of the aggregate, compound (A) / compound (B) = 1. / 20 to 20/1, preferably 1/20 to 4/1, more preferably 1/3 to 2/1, and particularly preferably 1/1 to 2/3.

  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 examples thereof include cement and gypsum. Preferred are cements such as ordinary Portland cement, high belite cement, medium heat cement, early-strength cement, ultra-high strength cement, sulfuric acid resistant cement, blast furnace slag cement, fly ash cement and the like. Further, in the hydraulic composition of the present invention, particularly the self-leveling material composition, the water / hydraulic powder ratio [weight percentage of water and powder in slurry (wt%), usually abbreviated as W / P. However, when the hydraulic powder is cement, it is abbreviated as W / C. ] Is preferably 50% by weight or less, more preferably 30 to 50% by weight, and particularly preferably 35 to 45% by weight.

Further, in the hydraulic composition of the present invention, particularly the self-leveling material composition, the weight ratio of the slag fine aggregate to the hydraulic powder is as follows: slag fine aggregate / hydraulic powder = 1 to 3; 2 or 2 is preferable in terms of fluidity and properties in a fresh state. Moreover, it is preferable from the point of workability | operativity that the compounding quantity of slag aggregate is 35 volume% or more in a composition, and also 37.5-47.5 volume%. In addition, the volume% of the slag fine aggregate in the composition is obtained by dividing 100 by the value obtained by dividing the weight (kg) of the slag fine aggregate in the composition 1 m ^{3 by} the density (kg / m ³ ) of the slag fine aggregate. It can be obtained by riding.

  The hydraulic composition of the present invention, particularly the self-leveling material composition, may contain a dispersant. Dispersants include lignin sulfonate and its derivatives as water reducing agents, oxycarboxylates, polyol derivatives, high-performance water reducing agents and high-performance AE water reducing agents such as naphthalene (manufactured by Kao Corporation: Mighty 150), melamine (Kao Co., Ltd. product: Mighty 150V-2), polycarboxylic acid type surfactants, polycarboxylic acid type surfactants (manufactured by Kao Co., Ltd .: Poise series) and the like can be mentioned. Among them, polycarboxylic acid-based high-performance water reducing agents and polycarboxylic acid-type surfactants, among them carboxylic acid-based monomers and one-end alkyl-capped polyethylene glycol (average number of moles of added ethylene oxide of 5 to 150) (meth) acrylic acid ester A copolymer with a monomer is preferred in the sense that both the fluidity and viscosity of the slurry can be achieved. Examples of the polycarboxylic acid dispersant include Kao Corporation: Mighty 3000, NMB: Leo Build SP, Nippon Shokubai Co., Ltd .: Aqualock FC600, Aqualock FC900, and the like.

  In addition to the compound (A) and the compound (B) contained in the hydraulic composition of the present invention, in particular, the self-leveling material composition, an existing thickener can be used. Examples of other existing thickeners include cellulose derivatives, polyacrylic polymers, polyethylene oxide, polyvinyl alcohol, gum polysaccharides, and microbial fermentation polysaccharides.

  The hydraulic composition of the present invention, particularly the composition for a self-leveling material, may be other components such as an AE agent, a retarding agent, an early strengthening agent, an accelerator, a foaming agent, and a foaming agent as long as the performance of the agent is not impaired. Further, it may contain an antifoaming agent, a rust preventive agent, a colorant, an antifungal agent, a crack reducing agent, a swelling agent, a dye, a pigment, a water absorbent resin, a water absorbent polymer, a water absorbent fiber and the like.

  Aggregates can be mixed in the hydraulic composition of the present invention, particularly the composition for a self-leveling material, and other fine aggregates and coarse aggregates can be used as the aggregate, and are not particularly limited. However, those having low water absorption and high aggregate strength are preferred. Coarse aggregates include rivers, land, mountains, sea, lime gravel, crushed stones, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural) and recycled coarse aggregate Can be mentioned. Examples of the fine aggregate include rivers, land, mountains, sea, lime sand, quartz sand and crushed sand thereof, lightweight fine aggregates (artificial and natural), and regenerated fine aggregates. In the hydraulic composition of the present invention, particularly the self-leveling material composition, the ratio of the slag fine aggregate is 50% in the total fine aggregate (in the total of the slag fine aggregate and other fine aggregates). 100% by weight is preferred. Here, the slag fine aggregate can be distinguished from other fine aggregates based on the slag aggregate composition and chemical component analysis method described in JIS A 5011-1, 2, 3.

  In the present invention, the self-leveling material is used to adjust the floor base of a building and the top end of the foundation horizontally among hydraulic compositions containing hydraulic powder such as cement and water. Since it is a material and requires high fluidity and fast curing, the unit water amount during compounding is generally not so high. Due to these properties, it is distinguished from a hydraulic composition having a relatively high unit water amount, for example, as disclosed in Patent Document 5.

<Method for producing hydraulic composition>
The hydraulic composition of the present invention, particularly the self-leveling material composition, is prepared by mixing the compound (A) and the compound (B) selected in a specific combination with water, hydraulic powder, and slag fine aggregate. It is obtained by doing. At that time, the amount of air is preferably 0.5 to 6% by volume, more preferably 1 to 3% by volume, and the slag fine aggregate is 35% by volume or more, preferably 37.%, based on the volume of the hydraulic composition. 5 to 47.5% by volume. Moreover, it is preferable that the quantity of hydraulic powder shall be 500-1000 kg / m < ³ >, and also 600-850 kg / m < ³ > on the volume basis of a hydraulic composition. Moreover, it is preferable to use hydraulic powder and slag fine aggregate by the weight ratio of slag fine aggregate / hydraulic powder = 1-3, and also 1.2-2. The W / P is preferably 50% by weight or less, more preferably 30 to 50% by weight, and particularly preferably 35 to 45% by weight. The hydraulic composition of the present invention, particularly the composition for the self-leveling material, is prepared by mixing these materials and air (gas which becomes a bubble source), and further, if necessary, other materials so that the total amount becomes 100% by volume. Can be obtained.

  The hydraulic composition of the present invention, particularly the self-leveling material composition, is produced through a process of mixing the compound (A) and the compound (B) with water, hydraulic powder, and slag fine aggregate. Can do. In that case, the compound (A) and the compound (B) may be added simultaneously or separately, but after mixing materials other than the compound (A), adding the compound (A) This is preferable from the viewpoint of controlling the amount of air taken.

(Method for preparing composition for self-leveling material)
Using the compound (A) and the compound (B) shown in Table 1, water, powder, aggregate and a predetermined amount of the compound (B) were mixed at a low speed of 63 rpm with a mortar mixer in accordance with the composition of the self-leveling material composition shown in Table 2. Then, after stirring for 30 seconds, a predetermined amount of the compound (A) was added and stirred for 60 seconds to prepare a composition for a self-leveling material.

(Note) The components in Table 2 are as follows.
Water (W): Tap water Cement (C): Ordinary Portland cement, commercially available, density 3.16 g / cm ³
・ Fine Aggregate (S): Blast Furnace Slag Fine Aggregate, Nippon Steel Corp. Nagoya Steel Works, Surface Dry Density 2.72 g / cm ³

(Measurement item)
The following evaluation was performed about the obtained composition for self-leveling materials. The results are shown in Table 3.

(1) Fluidity and fluidity retention A cone having a diameter of 50 mm and a height of 50 mm was used, and the flow values were measured immediately after production, 1 hour and 3 hours later. The amount of the high-performance water reducing agent was adjusted, and the initial mortar flow value was 200 ± 10 mm.

(2) Breathing water amount measurement 300 mL of the kneaded composition for a self-leveling material was put into a 500 mL beaker and collected until no floating water was generated every 30 minutes. The final collected amount was measured and evaluated according to the following criteria.
A: Final collection amount is 0 mL
○: Final collection amount is less than 5 mL Δ: Final collection amount is 5 mL or more and 50 mL or less ×: Final collection amount is more than 50 mL

(3) Dimensional stability after curing 500 mL of the produced self-leveling material composition was put into a bat made of enamel having a length of 25 cm, a width of 20 cm, and a height of 3.5 cm. The vacancies between the mortar and the bat were evaluated according to the following criteria.
○: No gap. The hardened body does not fall from the bat even if it is turned over.
X: A gap of about 0.5 to 1 mm is formed, and when turned over, the cured body is detached from the bat.

(4) Viscosity J14 funnel flow time (seconds) was measured. Good properties are between 10 seconds and 12 seconds.

(note)
* 1: The thickening of the mixed aqueous solution is carried out with the aqueous solution S _A of the compound (A) (having a viscosity at 20 ° C. of 100 mPa · s or less) and the aqueous solution S _B of the compound (B) (the viscosity at 20 ° C. of 100 mPa · s). s or less) was measured at a viscosity of 20 ° C. of an aqueous solution mixed at a weight ratio of 50/50, and “○” indicates that it can be at least twice as high as the viscosity of any aqueous solution before mixing. did.
* 2: The weight% of the compounds (A) and (B) is the effective amount added.
* 3: The high-performance water reducing agent is a polycarboxylic acid-based high-performance water reducing agent [copolymer of methacrylic acid and methoxypolyethylene glycol / methacrylic acid ester (ethylene oxide average added mole number 7)]. It is cement weight%.

Claims (9)

A cationic surfactant (hereinafter referred to as compound (A)), one or more compounds selected from the group consisting of an anionic aromatic compound and bromide compound (hereinafter referred to as compound (B)), water, A hydraulic composition containing hydraulic powder and slag fine aggregate,
The combination of the compound (A) and the compound (B) is an aqueous solution S _A of the compound (A) (having a viscosity at 20 ° C. of 100 mPa · s or less) and an aqueous solution S _B of the compound (B) (viscosity at 20 ° C. Is a combination in which the viscosity at 20 ° C. of an aqueous solution mixed with a 50/50 weight ratio is at least twice as high as the viscosity of any aqueous solution (20 ° C.) before mixing. Hard composition.   The slag fine aggregate and the hydraulic powder are contained in a weight ratio of slag fine aggregate / hydraulic powder = 1 to 3, and the blending amount of the slag aggregate is 35% by volume or more in the composition. Item 1. The hydraulic composition according to Item 1.   The hydraulic composition according to any one of claims 1 to 3, wherein the slag fine aggregate is a blast furnace slag fine aggregate.   The hydraulic composition according to any one of claims 1 to 3, wherein the hydraulic composition is a self-leveling material.   A cured product obtained by curing the hydraulic composition according to any one of claims 1 to 4. Cationic surfactant (hereinafter referred to as compound (A)) and one or more compounds selected from the group consisting of an anionic aromatic compound and bromide compound (hereinafter referred to as compound (B)), water, A hydraulic powder and a method for producing a hydraulic composition having a step of mixing with slag fine aggregate,
The combination of the compound (A) and the compound (B) is an aqueous solution S _A of the compound (A) (having a viscosity at 20 ° C. of 100 mPa · s or less) and an aqueous solution S _B of the compound (B) (viscosity at 20 ° C. Is a combination in which the viscosity at 20 ° C. of an aqueous solution mixed with a 50/50 weight ratio is at least twice as high as the viscosity of any aqueous solution (20 ° C.) before mixing. A method for producing a hydraulic composition.   The production method according to claim 6, wherein the slag fine aggregate is used in an amount of 35% by volume or more in the mixture.   The manufacturing method of Claim 6 or 7 which uses hydraulic powder and slag fine aggregate in the quantity used as the weight ratio of slag fine aggregate / hydraulic powder = 1-3.   The method according to any one of claims 6 to 8, wherein the hydraulic composition is a self-leveling material.