JPH10231165A - Self-flowing hydraulic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the quick-curing property and workability and enable preferable use as a self-leveling material, by compounding alumina cement, gypsum and blast furnace slag and aluminum sulfate and lithium salt, a polymer emulsion and a water reducing agent into a hydraulic composition. SOLUTION: Gypsum in an amount of 25-120 pts.wt. and blast furnace slag in an amount of 15-400 pts.wt. are added as a hydraulic component to 100 pts.wt. alumina cement. Further, 0.05-5wt.% total amount of aluminum sulfate and lithium salt as a setting modifier is added thereto and a molar ratio of aluminum sulfate to lithium carbonate is kept to 1-50. Further, 1-25 pts.wt. polymer emulsion and 0.1-5 pts.wt. water reducing agent are added thereto. As necessary, <=40 pts.wt. portland cement is added thereto. Control of the pot life of the composition can be carried out and use of the composition as a self-leveling material can be facilitated by simultaneously adding lithium salt of a setting accelerator and aluminum sulfate of setting retarder to the hydraulic component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is excellent as a self-leveling material used for preparing flooring materials for general buildings or as a colorable floor finishing material for factories, warehouses, parking lots, gas stations, kitchens and the like. Self-flowing hydraulic composition having improved properties.

[0002]

2. Description of the Related Art It is a matter of course that the first condition that a hydraulic composition to be used as a self-leveling material should have is a high fluidity necessary to secure self-leveling, It is also required that the material has a sufficient quick-hardening property to enable the work, and that an appropriate pot life can be obtained from the viewpoint of facilitating the construction work. Further, it is necessary that the properties of the cured product after curing, such as strength, surface properties, dimensional stability, and chemical resistance including water resistance, are high. Many technologies have already been disclosed for hydraulic compositions used as self-leveling materials, but in order to satisfy these multiple requirements that self-leveling materials should have, many of the disclosed technologies require rapid hardening hydraulics. It has a complicated composition in which a fluidizing agent and a setting modifier are added to the components to control the fluidity and setting rate, and further, a plurality of admixtures such as a thickener and an antifoaming agent are added.

For example, Japanese Patent Application Laid-Open No. 61-155241 discloses a method of adding sodium sulfate, potassium sulfate, and aluminum sulfate as a setting accelerator to a hydraulic component consisting of hydrofluoric anhydride gypsum, blast furnace slag, and calcium silicate. A self-leveling material comprising a water reducing agent, an antifoaming agent, a water retention agent, and a polymer emulsion is disclosed. Japanese Patent Application Laid-Open No. 5-9049 discloses that at least one kind selected from magnesium carbonate, calcium aluminate and aluminum sulfate is added as a setting accelerator to various portland cements or mixed cements, and a water reducing material and a thickening agent are further added. Compositions having an added composition are disclosed. 6-81
In Japanese Patent No. 97, too, oxycarboxylic acid (salt), alkali carbonate or alkali bicarbonate, phosphate or the like is used as a setting retarder for the hydraulic component consisting of blast furnace slag, calcium aluminate and gypsum in order to control the setting speed. It is disclosed that a polymer emulsion is further added to the added one. Further, Japanese Unexamined Patent Application Publication No. 8-217508
In the publication, a cement hardening agent comprising calcium aluminate and an alkali or alkaline earth metal sulfate, and an oxycarboxylic acid (salt) -based organic substance and / or calcium hydroxide, aluminate, alkali carbonate, etc. There is disclosed a composition in which an inorganic compound is added as a setting retarder to adjust the setting rate, and in which various known fluidizing agents and antifoaming agents are added.

[0004] Although the techniques disclosed so far show some improvement effects, further improvements are necessary in view of all aspects of quick-hardening properties, working characteristics and cured body characteristics.
There has been a strong need for the development of materials that allow for light walking and surface finishing on the day of construction without sacrificing other properties.

[0005]

DISCLOSURE OF THE INVENTION The present invention is excellent in quick-setting properties, working properties (high fluidity, long pot life) and curing properties (high strength, high abrasion resistance, high smoothness, coloring possibility). Another object of the present invention is to provide a self-flowing hydraulic composition that can be suitably used as a self-leveling material.

[0006]

Means for Solving the Problems The inventors of the present invention have developed a hydraulic component having essentially rapid hardening properties and excellent curing properties;
The present inventors have found that a composition comprising a suitable setting regulator, a polymer emulsion and a fluidity improver is a composition which solves the above-mentioned problems, and completed the present invention. That is, the present invention relates to a hydraulic component composed of alumina cement, gypsum and blast furnace slag, a setting regulator composed of aluminum sulfate and lithium salt, a polymer emulsion, and a self-fluid hydraulic composition composed of a water reducing agent. Hereinafter, the present invention will be described in detail.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Self-flowing hydraulic compositions used as self-leveling materials are roughly classified into two types, gypsum-based and cement-based, according to hydraulic components. The gypsum system has the advantages that it has good dimensional stability and cures in a short time, but has the drawback that peeling and rust easily occur and water resistance is low. On the other hand, cement systems have the advantages of high water resistance and high surface hardness,
Generally, Portland cement systems have the disadvantage that curing speed is low and drying shrinkage is large, while fast-setting cement systems have the disadvantage of improving curing speed, but have the disadvantage of low fluidity and low workability. Have. In the present invention, the use of a hydraulic component consisting of alumina cement, gypsum and blast furnace slag compensates for each other's drawbacks and solves this problem.

[0008] Alumina cement has potentially rapid hardening properties, and after hardening, gives a cured product having excellent chemical resistance and fire resistance. In addition, the presence of the blast furnace slag having latent hydraulic property also suppresses a drawback of the blast furnace slag, which is a drawback, with time, in the strength of the cured product. Furthermore, in the presence of sulfate, calcium sulphoaluminate hydrate and the like are generated, and the rate of water reduction in the cured product increases, thereby enabling finishing work on the construction day.
Several types of alumina cements having different mineral compositions are known and commercially available, but the main component is monocalcium aluminate (CA), and commercially available products can be used regardless of the type.

Gypsum is inherently quick-hardening and is a necessary component for maintaining dimensional stability after curing. The amount of gypsum added is 25 to 1 per 100 parts by weight of alumina cement.
20 parts by weight, preferably 40 to 100 parts by weight. If the amount is less than 25 parts by weight, the dimensional stability decreases, and 1
If the amount is more than 20 parts by weight, the water resistance decreases, and abnormal expansion due to water may occur, which is not preferable. In addition, gypsum can be used alone or as a mixture of two or more gypsums, such as anhydrous and hemihydrate, irrespective of their types.

Since the blast furnace slag has a small drying shrinkage, it has an effect of improving not only the crack resistance of the cured product but also the strength of the cured product of alumina cement. In addition, it also has an effect of suppressing a decrease in strength due to the transition of alumina cement hydrate. The amount of blast furnace slag is 15 to 40 with respect to 100 parts by weight of alumina cement.
0 parts by weight, preferably 50 to 300 parts by weight. Fifteen
When the amount is less than the weight part, the shrinkage becomes large and
If the amount is larger than the weight part, the strength may be reduced. Hydraulic components consisting of the components described here have potentially rapid hardening properties, and the following setting modifiers are added,
By controlling the setting speed to a condition suitable for construction, it is possible to obtain an initial strength capable of light walking one and a half hours after construction, and to start finishing material construction four hours later.

Portland cement can be further added to the hydraulic component consisting of alumina cement, gypsum and blast furnace slag. The addition of low-cost Portland cement is effective in reducing the cost of self-leveling materials,
If the amount is too large, the fluidity decreases, so the amount added is
It is preferable to use less than 40 parts by weight based on 100 parts by weight of alumina cement.

Another important requirement of the self-leveling material is that it has a reasonable pot life. In the present invention, it has been found that the pot life can be adjusted by simultaneously adding a lithium salt as a setting accelerator and aluminum sulfate as a setting retarder to the hydraulic component described above. FIG. 1 shows an example showing the effect of adding lithium carbonate as a kind of lithium salt and aluminum sulfate on the hydration reaction of alumina cement. In FIG. 1, the horizontal axis represents the elapsed time after component kneading, and the vertical axis represents the calorific value accompanying the hydration reaction, and the exothermic peak indicates that the hydration reaction, that is, the coagulation is progressing at that time. . With alumina cement alone, the maximum exothermic peak exists after 300 minutes and the setting is very slow, but the addition of lithium carbonate shifts the maximum exothermic peak to about 90 minutes, indicating that the setting is greatly accelerated. However, the heat generation peak after about 20 minutes is large, and the fluidity is greatly reduced due to the coagulation reaction that generates this heat generation, and it is difficult to secure a sufficient pot life. On the other hand, when aluminum sulfate is further added, the maximum peak shifts to the long-term side by about 30 minutes and the coagulation is slightly delayed, but the exothermic peak after 20 minutes also becomes small, and the fluidity due to the coagulation reaction that produces this exothermic peak is reduced. Is suppressed,
Sufficient pot life can be secured.

[0013] It is known that a lithium compound has an effect of accelerating the setting of alumina cement. However, the effect is very large. This is an advantage that a sufficient effect can be obtained even if a small amount is added. This is a negative factor that mixing is difficult and that it is difficult to control the pot life with good reproducibility under conditions suitable for construction.
On the other hand, it is known that aluminum sulfate has an action as a setting accelerator for hydraulic substances such as various cements and gypsum. For example, as described in JP-A-61-1
Nos. 55241 and 5-9049 describe the addition of aluminum sulfate as a setting accelerator. This aluminum sulfate acts as a setting retarder for the hydraulic component mainly composed of alumina cement, and exerts a great effect on the control of the setting speed of the hydraulic component when used in combination with the lithium salt which is a setting accelerator. This is the first time that the present invention has obtained the knowledge.

The lithium salts usable in the present invention include:
Inorganic acid salts such as lithium carbonate, lithium chloride, lithium sulfate, lithium nitrate, lithium hydroxide and the like, and organic acid salts such as lithium acetate, lithium acetate, lithium tartrate, lithium malate, lithium citrate, lithium glycolate and the like. Although it is possible, use of lithium carbonate is particularly preferable. On the other hand, examples of aluminum sulfate include aluminum sulfate having anhydrous or various water contents and various alums containing aluminum sulfate.

As described above, in the present invention, by simultaneously adding a lithium salt as a setting accelerator and aluminum sulfate as a setting retarder to the hydraulic component,
Adjusts the pot life and facilitates use as a self-leveling material. Therefore, the ratio of the setting accelerator to the setting retarder, that is, the ratio of aluminum sulfate to lithium carbonate, is a major factor that affects the properties of the self-leveling material of the present invention. In the present invention, the molar ratio of aluminum sulfate to lithium salt is preferably in the range of 1 to 50. If the molar ratio of aluminum sulfate to lithium salt is less than 1, coagulation is too fast and self-fluidity is reduced, so that the pot life becomes too short and hinders construction,
On the other hand, if it is larger than 50, the quick-hardening property is reduced, and it is difficult to open it early.

In the present invention, the use of a coagulation adjusting agent in which a lithium compound and aluminum sulfate are used in combination can also provide an effect of enabling coloring. That is,
Since the separation of materials can be reduced by promoting the coagulation by the lithium compound, color unevenness is less likely to occur. Further, even if color unevenness occurs, a sufficient flow holding time can be secured by adding aluminum sulfate, so that it can be easily removed by a surface treatment operation using a register mark.

In addition to the above-mentioned aluminum sulfate and lithium salt, oxycarboxylic acids such as tartaric acid, citric acid, malic acid, glycolic acid and the like, or alkali metal salts and alkaline earth metals thereof, which have a conventionally known set retarding action. One or more salts may be added. The amount of the oxycarboxylic acid or a salt thereof is 0.5 parts by weight or less per 100 parts by weight of the hydraulic component. When the amount of addition is large, surface defects may occur due to a decrease in fluidity, poor curing, and accompanying generation of breathing water.

The most basic factor that the self-leveling material should have is high fluidity. In order to suppress material separation and obtain a high-strength cured product, it is necessary to lower the water / hydraulic component ratio. However, even if the water / hydraulic component is lowered, high flowability is ensured. Need to be added. Especially,
Since the expression strength of alumina cement, which is one of the hydraulic components in the present invention, is greatly affected by the water / cement ratio, it is essential to reduce the water / hydraulic component ratio by using a water reducing agent. . As the water reducing agent, commercially available products such as naphthalene-based, melamine-based, and polycarboxylic acid-based products can be used irrespective of the type, but in terms of quantity, the effect is not sufficiently exhibited when the amount is too small, and the amount is too large. However, since the effect corresponding to the added amount cannot be expected and the economy is not only zero, but also causes poor curing, the added amount is preferably 0.1 to 5 parts by weight per 100 parts by weight of the hydraulic component.

The self-flowing hydraulic composition of the present invention, by further adding a polymer emulsion, not only improves the adhesion to the underlying concrete and the crack resistance, but also increases the wear resistance of the cured product. It is possible,
It can be used as a finishing material. Polymer emulsions, for example, ethylene-vinyl acetate, styrene-butadiene, acrylonitrile-butadiene and other copolymers,
Alternatively, a commercially available product such as a homopolymer such as polybutene, polyvinyl chloride, polyacrylate, or polyvinyl acetate can be used regardless of the type. The addition amount of the polymer emulsion is preferably 1 to 25 parts by weight per 100 parts by weight of the hydraulic component. If the amount is too small, a sufficient effect will not be exhibited. If the amount is too large, not only will the flowability be reduced, but also air bubbles will be entrained to deteriorate the surface condition of the cured product, resulting in reduced strength.

By making the above-mentioned hydraulic component, setting regulator, water reducing agent and polymer emulsion essential components,
Not only has excellent fluidity, but also has a pot life of 10 minutes to 3
It can be adjusted during 0 minutes, and it is possible to obtain a self-leveling material having excellent cured body properties.
In addition to the above essential components, it is preferable to add an antifoaming agent and a thickener as necessary. Defoamers and thickeners are added
It suppresses the separation of aggregates and the generation of bubbles on the surface of the cured product, and has a favorable effect on improving the appearance of the cured product. As the defoaming agent, a known substance such as a silicone-based, alcohol-based, polyether-based synthetic substance or a plant-derived natural substance can be used, and as the thickener, methylcellulose,
Known substances such as cellulosics such as carboxymethylcellulose, protein types such as casein, gelatin, pectin, latex types such as natural rubber and styrene-butadiene rubber, and water-soluble polymer types such as polyethylene glycol, polyacrylamodo and polyvinyl alcohol Can be used. The amounts of the defoaming agent and the thickener are preferably 2 parts by weight or less and 1 part by weight or less with respect to 100 parts by weight of the hydraulic component. Even if the defoaming agent is added in an amount of more than 2 parts by weight, no further increase in the defoaming effect is observed, and when the amount of the thickener is too large, there is a possibility that the fluidity is reduced.

The self-flowing hydraulic composition of the present invention may further contain known extenders such as fly ash, limestone powder, and siliceous powder. By adding a filler,
Although the fluidity is improved and a favorable result is obtained, if the addition amount is too large, the strength development is reduced. Therefore, the addition amount is desirably 200 parts by weight or less per 100 parts by weight of the hydraulic component. The size is preferably 45 mm or less from the viewpoint of the effect.

The self-flowing hydraulic composition according to the present invention comprises
Although it can be used as a cement paste kneaded with water, it is used by adding various aggregates and / or fillers and utilizing the properties thereof. As the aggregate, silica sand, river sand, sea sand, blast furnace slag, and various crushed stones can be used, but the diameter is desirably 2 mm or less. The amount of aggregate added is 200 per 100 parts by weight of the hydraulic component.
It is desirable to use not more than parts by weight. When the amount is more than 200 parts by weight, not only does the fluidity decrease, but also the strength developability may decrease.

[0023]

The present invention will be described in more detail with reference to specific examples. Examples 1 to 6 and Comparative Examples 1 to 7 (1) Raw Materials Used In carrying out each example, the following raw materials were used. Alumina cement: Blaine specific surface area: 3,000 cm ² / g Monocalcium aluminate content: 45% by weight Gypsum: Type II anhydrous gypsum, Blaine specific surface area: 4,000 cm ² / g Blast furnace slag: Blaine specific surface area: 4,500 cm ² / g sulfuric acid Aluminum: Anhydride Commercially available Lithium carbonate: Commercially available Water reducing agent: Melamine-based dispersant, Commercially available Polymer emulsion: Ethylene-vinyl acetate copolymer resin powder, Commercially available thickener: Methylcellulose-based thickener, Commercially available Foaming agent: Silicone antifoaming agent, commercially available Aggregate: No. 6 silica sand

(2) Preparation of Hydraulic Composition and Mortar Specimen As a hydraulic composition component, a predetermined amount of a curing rate adjuster, a water reducing agent, A mortar specimen was obtained by adding 100 parts by weight of aggregate and 44 parts by weight of water to a polymer emulsion, and further adding a thickener and an antifoaming agent as needed, and kneading the mixture for 3 minutes. Table 1 shows the mixing ratio of each component in each example.

(3) Measurement of Properties of Mortar The following measurement was performed on the formed mortar specimen, and the properties of the self-flowing hydraulic composition were evaluated. Table 2 shows each measurement item from the viewpoint of practicality as a self-leveling material.
The criteria for pass / fail shown in (1) are provided. Flow value: Measured according to JASS 15M-103. Compressive strength: 4 × 4 × 1 specified in JIS R5201
Mortar is packed in a 6mm mold at 20 ° C and 80% humidity.
% For 3 hours in air, then demolded and further air (20 ° C,
A molded article additionally cured for a predetermined period of time in water (80% humidity) or water (cured for 1 day in air at 20 ° C. and 80% humidity) and further cured in water at 20 ° C. according to JIS R5
The measurement was performed according to the method described in No. 201. Length change rate: 4 × 4 × specified in JIS R5201
Mortar is packed in a 16mm mold at 20 ° C, humidity 8
The molded product obtained by removing the mold after air curing at 0% for one day was measured by the comparator method described in JISS A1125. Drying days: The kneaded mortar was poured at a thickness of 10 mm onto a 300 × 300 mm concrete plate and cured, and the surface moisture was measured with a ket moisture meter. The number of days required for the surface moisture to become 8% or less was defined as the number of dry days. Abrasion loss: The kneaded mortar is 100 mm wide x 7 long.
mm in a 10 mm thick mold at 20 ° C and 80% humidity.
% For 7 days in air, and the molded body obtained by demolding was used as a sample, and the amount of wear loss was measured using a Daver abrasion tester (test condition: wear wheel model H-22, overload 250 g, rotation number 2000 times). Was measured. Color unevenness: ₃ parts of mortar obtained by adding 2 parts by weight of Fe ₂ O ₃ red pigment as an additional component to 100 parts by weight of hydraulic component
The mixture was poured into a 00 × 300 mm concrete plate at a thickness of 10 mm, cured at 20 ° C. and a humidity of 65% for 28 days, and then visually observed. Those in which color unevenness was not observed were evaluated as good, and those in which color unevenness was observed were evaluated as poor. Table 2 shows the measurement results of the mortar characteristics.

[0026]

[Table 1]

[0027]

[Table 2]

The results in Table 2 show that the compositions having compositions falling within the scope of the present invention satisfy the criteria for all items and have excellent properties as self-leveling materials. On the other hand, in a composition having a composition out of the range of the present invention, even if the criteria are cleared in some items, the criteria cannot be cleared in other items, and the composition is not suitable as a self-leveling material requiring a plurality of functions. It is shown that.

[0029]

The self-flowing hydraulic composition of the present invention not only has a sufficient flowability as a self-leveling material, but also has a sufficient flow holding time, so that the workability of the setting work can be ensured. In addition to being excellent in hardness, it is also excellent in quick-hardening and quick-drying properties, so that it is possible to shorten the construction period, for example, light walking and surface finishing on the day of construction. In addition, wear resistance,
It has excellent dimensional stability properties and cured body properties such as strength, and can be used as a direct finishing material. In addition, it is possible to color evenly.

[Brief description of the drawings]

FIG. 1 is a diagram showing the effects of lithium carbonate and aluminum sulfate on the hydration reaction of alumina cement.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // C04B 111: 62

Claims (10)

[Claims] 1. A hydraulic component consisting of alumina cement, gypsum and blast furnace slag, a setting regulator consisting of aluminum sulfate and a lithium salt, a polymer emulsion, and
A self-flowing hydraulic composition comprising a water reducing agent. 2. The self-flowing hydraulic composition according to claim 1, wherein the hydraulic component comprises 25 to 120 parts by weight of gypsum and 15 to 400 parts by weight of blast furnace slag based on 100 parts by weight of alumina cement. 3. The self-flowing liquid according to claim 1, wherein the lithium salt is lithium carbonate, lithium chloride, lithium sulfate, lithium nitrate, lithium hydroxide, lithium acetate, lithium tartrate, lithium malate or lithium citrate. Hydraulic composition. 4. The self-flowing hydraulic composition according to claim 1, wherein the molar ratio of aluminum sulfate to lithium salt is from 1 to 50. 5. The combined amount of aluminum sulfate and lithium salt is as follows:
The self-flowing hydraulic composition according to any one of claims 1 to 4, wherein the amount is 0.05 to 5 parts by weight based on 100 parts by weight of the hydraulic component. 6. The amount of the hydraulic component 1
The self-flowing hydraulic composition according to any one of claims 1 to 5, which is 1 to 25 parts by weight based on 00 parts by weight. 7. The self-flowing hydraulic composition according to claim 1, wherein the amount of the water reducing agent is 0.1 to 5 parts by weight based on 100 parts by weight of the hydraulic component. 8. A hydraulic component comprising aluminum cement, gypsum and blast furnace slag in a proportion of 25 to 120 parts by weight of gypsum and 15 to 400 parts by weight of blast furnace slag to 100 parts by weight of alumina cement, aluminum sulfate and lithium carbonate. A coagulation modifier, wherein the total amount of aluminum and lithium carbonate is 0.05 to 5 parts by weight with respect to 100 parts by weight of the hydraulic component, and the molar ratio of aluminum sulfate to lithium carbonate is 1 to 50; 10
1 to 25 parts by weight of the polymer emulsion based on 0 parts by weight, and 0.1 to 100 parts by weight of the hydraulic component.
A self-flowing hydraulic composition comprising 5 parts by weight of a water reducing agent. 9. The self-flowing hydraulic composition according to any one of claims 1 to 8, further comprising one or more selected from a thickener, an antifoaming agent and a filler. Self-flowing hydraulic composition comprising: 10. A mortar or concrete obtained by further adding an aggregate and water to the self-flowing hydraulic composition according to any one of claims 1 to 9.