JP3478108B2 - Hydraulic coloring finishing material composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored floor finish having both ultra-fast curing property and self-leveling property. Specifically, a hydraulic coloring finish material composition having super-fast curing and self-leveling properties, which enables simultaneous adjustment of floor base and coloring finish in factories, warehouses, parking lots, gas stations, kitchens, etc. It is about.

[0002]

Many techniques have already been disclosed for compositions having self-leveling properties. For example, Japanese Patent Laid-Open No. 61-155241, Japanese Patent Laid-Open No. 5-9049, Japanese Patent Publication No. 6-8197, and Japanese Patent Laid-Open No. 8-217508 disclose high fluidity and construction work for ensuring self-leveling. Composition for the purpose of improving the property of a cured product after curing for an appropriate period of time, and strength, surface properties, dimensional stability, chemical resistance including water resistance, etc. Is disclosed. However, these compositions do not satisfy all of the properties required as a floor base conditioner,
In particular, it is far from the technical level that the casting surface can be used as it is as a floor finishing material due to poor coloring property such as occurrence of color unevenness, and therefore, on the floor base cured product obtained from the self-leveling composition, Ceramic tile, P-tile,
It was necessary to apply colored finishing materials such as sheets and finishing paints.

[0003]

DISCLOSURE OF THE INVENTION The present invention is not only excellent in quick-hardening property, working property (high fluidity, long pot life) and hardening property (high strength, high abrasion resistance, high smoothness). It is also an object of the present invention to provide a hydraulic coloring finishing material composition which is excellent in colorability and is capable of simultaneously adjusting a floor base and finishing coloring color.

[0004]

The inventors of the present invention have found that a hydraulic component essentially having a rapid hardening property and having an excellent hardening property, a suitable coagulation modifier, a polymer emulsion and a fluidity improving agent. The present invention has been completed by finding that a composition in which a pigment, a thickener and an antifoaming agent are further combined with the composition consisting of the above is a composition in which the above problems are solved. That is,
The present invention is an alumina cement, a hydraulic component consisting of gypsum and blast furnace slag, a setting regulator consisting of aluminum sulfates and a lithium salt, a polymer emulsion, a water reducing agent,
The present invention relates to a hydraulic coloring finish composition comprising a pigment, a thickener, and a defoaming agent. The present invention will be described in detail below.

One of the important requirements that the self-leveling material must have is that it has an appropriate rapid hardening property, which is primarily dependent on the type of hydraulic component contained. When the self-leveling material is roughly classified according to the hydraulic component, there are two types, a gypsum type and a cement type. The plaster system is
Although it has good dimensional stability and has the advantage that it cures in a short time, it has the drawback that peeling and rusting of the steel frame easily occur and the water resistance is low, while the cement system has high water resistance, Although it has the advantage of high surface hardness, it usually has the drawbacks that the curing rate is low and the drying shrinkage is large in the cement type Portland cement system. It has the disadvantage of low workability and low workability. That is, both systems have a problem that needs to be improved when they are used as a floor base conditioner. Further, a problem common to both systems is that material separation occurs before curing. This material separation promotes segregation of the added pigment and causes color unevenness after curing, which is a fatal drawback in using the self-leveling material as a coloring finishing material. In addition, in the conventional cement-based cement, efflorescence caused by calcium hydroxide generated by the hydration reaction was generated, and when it was colored, it was conspicuous. In the present invention, these problems are solved by using a hydraulic component composed of alumina cement, gypsum and blast furnace slag.

Alumina cement has a potential for rapid hardening and, after hardening, gives a hardened material having excellent chemical resistance and fire resistance. In addition, the presence of the blast furnace slag having latent hydraulicity also suppresses the disadvantage thereof, that is, the deterioration of the strength of the cured body over time. Although several kinds of alumina cements having different mineral compositions are known and commercially available, the main component is monocalcium aluminate (CA), and commercially available products can be used regardless of the type. Moreover, calcium hydroxide, which causes the generation of sinter in conventional cement systems, is not generated.

[0007] Gypsum has a rapid hardening property and is a component necessary for maintaining the dimensional stability after hardening. The addition amount is 25 to 120 parts by weight, preferably 40 to 100 parts by weight per 100 parts by weight of alumina cement. 100 parts by weight is preferable. Two
If it is less than 5 parts by weight, the dimensional stability will be reduced, and if it is more than 120 parts by weight, the water resistance will be reduced and abnormal expansion due to water may occur, which is not preferable. As for gypsum, regardless of the type of gypsum such as anhydrous or semi-water, one type or a mixture of two or more types can be used.

Since blast furnace slag has a small drying shrinkage, it has not only the effect of improving the crack resistance of the hardened product, but also the effect of improving the strength of the hardened product of alumina cement. Further, it also has an effect of suppressing the strength decrease due to the transition of the alumina cement hydrate. The amount of blast furnace slag is 15 to 400 parts by weight, preferably 50 to 300 parts by weight, based on 100 parts by weight of alumina cement. 1
If it is less than 5 parts by weight, the shrinkage will increase, and
If it is more than 0 parts by weight, the strength may decrease. The hydraulic component consisting of the components described here has a potential for rapid hardening.
By controlling the setting speed to a condition suitable for construction, it is possible to obtain an initial strength that enables light walking in 1 and a half hours after construction, and after 4 hours, finish material construction can be started if necessary. It will be possible. Even if a pigment is added, it is possible to completely prevent material separation at this curing speed (about 1 and a half hours). It can be done in a short time.

Portland cement may be further added to the hydraulic component composed of alumina cement, gypsum and blast furnace slag. Although the addition of low-priced Portland cement is effective in reducing the cost of hydraulic coloring finish materials,
If the amount is too large, not only the fluidity is deteriorated but also white fluff may be generated. Therefore, the addition amount is preferably less than 40 parts by weight with respect to 100 parts by weight of the alumina cement.

Another important requirement that the self-leveling material should have is that a proper pot life can be obtained. However, in the present invention, the hydraulic component described above contains a lithium salt as a setting accelerator and a setting agent. It has been found that the pot life as a colored floor finish can be adjusted by simultaneously adding aluminum sulfates as a retarder. That is, it was found that even if a pigment is added, it is possible to prevent pigment segregation caused by material separation and to completely prevent the occurrence of color unevenness by providing a quick-hardening property that does not impair workability, and finishes the self-leveling material. For the first time, it can be applied to wood.

An example showing the effect of adding lithium carbonate as a kind of lithium salt and anhydrous aluminum sulfate as aluminum sulfates to the hydration reaction of alumina cement is shown in FIG. In FIG. 1, the horizontal axis represents the elapsed time after kneading the components, and the vertical axis represents the amount of heat generated by the hydration reaction. The exothermic peak indicates that the hydration reaction, that is, the condensation is progressing at that time. . With alumina cement alone, the maximum exothermic peak exists after 300 minutes and the setting is very slow, but
It can be seen that the addition of lithium carbonate shifts the maximum exothermic peak to about 90 minutes, which significantly promotes coagulation. But,
The exothermic peak after about 20 minutes is also large, and the fluidity is greatly reduced by the condensation reaction that produces this exotherm, 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 time side for about 30 minutes and the condensation is slightly delayed, but the exothermic peak after 20 minutes also becomes small, and the fluidity due to the condensation reaction that produces this exothermic peak is reduced. It is possible to prevent the deterioration of the pot life and secure a sufficient pot life.

By controlling the mixing ratio of a lithium salt as a setting accelerator and a settling agent consisting of aluminum sulfates as a set retarder, the setting rate of a hydraulic component containing alumina cement as a main component can be controlled. It can be adjusted as desired, and a sufficient pot life can be ensured in consideration of workability with good reproducibility, and a floor finish without color unevenness can be obtained even if a pigment is added.

As described above, in the present invention, the pot life is adjusted by simultaneously adding the lithium salt as the setting accelerator and the aluminum sulfates as the setting retarder to the hydraulic component. The ratio of the setting accelerator to the setting retarder, that is, the mixing ratio of the aluminum sulfates and the lithium salt is a major factor that affects the setting speed of the hydraulic coloring finishing material composition and the prevention of color unevenness. 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, the setting will be too fast and the self-fluidity will decrease, and the working time will be too short, which will hinder the construction. This is because not only the hardness is deteriorated and it becomes difficult to open it early, but also material separation and color unevenness occur.

The lithium salt usable in the present invention includes:
Examples thereof include inorganic acid salts such as lithium carbonate, lithium chloride, lithium sulfate, lithium nitrate and lithium hydroxide, and organic acid salts such as lithium acetate, lithium acetate, lithium tartrate, lithium malate, lithium citrate and lithium glycolate. However, the use of lithium carbonate is particularly preferable. The particle size of the lithium salt used is preferably 50 μm or less. If the particle size is larger than 50 μm, the dissolution rate of the lithium salt will be low, and in the pigment-added system, many fine spots may be conspicuous and the appearance may be impaired.

On the other hand, examples of the aluminum sulfates usable in the present invention include anhydrous or various water contents of aluminum sulfate, alums such as potassium alum and sodium alum, and burnt alums obtained by heating and dehydrating alums. A double salt containing a sulfate group and an aluminum ion as components can be mentioned. These aluminum sulfates have a relatively high solubility in water, and those commercially available in powder form for industrial use can be used as they are.

In addition to the above-mentioned aluminum sulfates and lithium salts, oxycarboxylic acids such as tartaric acid, citric acid, malic acid and glycolic acid, which have been conventionally known to have a setting retarding effect,
Alternatively, one or more of the alkali metal salts and alkaline earth metal salts thereof may be added. The amount of oxycarboxylic acid or its salt added is 0.5 parts by weight or less per 100 parts by weight of the hydraulic component. If the addition amount is large, surface defects may occur due to deterioration of fluidity, curing failure and accompanying breathing water, which may further cause color unevenness.

The most basic factor that the self-leveling material should have is high fluidity. It is necessary to lower the water / hydraulic component ratio to suppress material separation and obtain a high-strength cured product, but a water-reducing agent is used to secure high fluidity even if the water / hydraulic component is lowered. Is required. In particular,
Since the expression strength of alumina cement, which is one of the hydraulic components in the present invention, is greatly influenced by the water / cement ratio, it is essential to use a water reducing agent to reduce the water / hydraulic component ratio. . As the water reducing agent, commercially available products such as naphthalene type, melamine type and polycarboxylic acid type can be used regardless of the type, but in terms of quantity, if the amount is too small, sufficient effect is not expressed, and there is too much. However, the effect corresponding to the added amount cannot be expected, which is uneconomical and causes curing failure. Therefore, the added amount is preferably 0.1 to 5 parts by weight per 100 parts by weight of the hydraulic component.

The addition of the polymer emulsion can improve not only the adhesiveness with the concrete foundation and the crack resistance but also the abrasion resistance of the hardened body, and is an essential component when used as a finishing material. . Polymer emulsions include, for example, ethylene-vinyl acetate, styrene-
Commercially available copolymers such as butadiene and acrylonitrile-budadiene, and homopolymers such as polybutene, polyvinyl chloride, polyacrylate and polyvinyl acetate can be used regardless of the type. The amount of the polymer emulsion added is 0.5 to 25 per 100 parts by weight of the hydraulic component.
It is good to use parts by weight. If the amount is too small, the sufficient effect is not expressed, and if the amount is too large, not only does the flowability decrease, but
The air bubbles may be entrained to deteriorate the surface state of the cured product, resulting in a decrease in strength.

By using the above-mentioned hydraulic component, setting regulator, water-reducing agent and polymer emulsion as components, not only excellent fluidity but also pot life of 10 to 30 minutes are obtained.
It is possible to obtain a self-leveling material composition which can be adjusted in a minute, that is, which has excellent characteristics. However, in the present invention, by further adding a pigment, a thickener and an antifoaming agent, self-leveling A hydraulic coloring finish material composition having properties can be obtained. The hydraulic coloring finishing material composition of the present invention contains a pigment as a component, but since segregation of the pigment during curing is completely prevented, a colored cured product having a uniform hue without color unevenness is formed. However, a colored cured product having an excellent aesthetic appearance can be obtained at the same time when the floor base is adjusted, without using a coloring finish material such as a conventionally used ceramic tile, P-tile, sheet or Juutan. Depending on the intended color, the pigment will be selected as an appropriate one that develops it, but from the intended use of the cured product, it is necessary that it has excellent alkali resistance and weather resistance. The use of pigments is preferred.
Inorganic pigments include, for example, titanium white, red iron oxide, yellow ocher, etc., iron, chromium, titanium,
Various colors containing cobalt and other various metal oxides, hydroxides or sulfides as main components are commercially available,
A commercially available product can be used alone or as a mixed color obtained by mixing a plurality of products. Further, the addition amount of the pigment is determined according to the desired color density, and in the case of adding the aggregate, the addition amount of the aggregate is also taken into consideration.
0.5 to 30 parts by weight is preferable with respect to parts by weight. A particularly preferable amount of the pigment added is 0.5 to 10 parts by weight with respect to 100 parts by weight of the hydraulic component, and, in the case of adding the aggregate, 100 parts by weight of the combined amount of the hydraulic component and the aggregate. Is the range. If the amount is less than 0.5 parts by weight, the coloring may be insufficient, while if the amount is more than 10 parts by weight, the improvement of the coloring effect commensurate with the addition amount cannot be expected.

The addition of the defoaming agent and the thickener suppresses the separation of aggregates and the generation of bubbles on the surface of the cured product, has a favorable effect on the improvement of the appearance of the cured product, and gives the properties as a hydraulic coloring finish material completely. Make something As the defoaming agent, known materials such as silicone-based, alcohol-based, polyether-based synthetic substances or plant-derived natural substances can be used, and the thickeners include cellulose such as methyl cellulose and carboxymethyl cellulose. Well-known materials such as system, protein system such as casein, gelatin, pectin, natural rubber, latex system such as styrene-butadiene rubber, water-soluble polymer system such as polyethylene glycol, polyacrylic amod, polyvinyl alcohol, etc. can be used. . The antifoaming agent and the thickening agent are preferably added in an amount of 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, the defoaming effect is not further increased, and if the amount of the thickening agent is too large, the fluidity may be lowered.

In addition to the above-mentioned essential components, the hydraulic coloring finish composition of the present invention further comprises fly ash, limestone powder,
A known extender such as siliceous powder can be added.
The addition of the extender improves the fluidity and gives preferable results. However, if the addition amount is too large, the strength development is deteriorated. Therefore, the addition amount is 2 per 100 parts by weight of the hydraulic component.
It is desirable that the amount is 00 parts by weight or less. Further, it is preferable that the size is 45 μm or less from the viewpoint of the effect.

The hydraulic colored finish composition according to the present invention comprises:
Although it can be used as a cement paste kneaded with water, the use of various aggregates and / or extenders is a method of utilizing its characteristics. As the aggregate, silica sand, river sand, sea sand, blast furnace slag, and various crushed stones can be used, but the diameter is preferably 2 mm or less. The amount of aggregate added is 200 per 100 parts by weight of the hydraulic component.
It is desirable that the amount is less than or equal to parts by weight. If the amount is more than 200 parts by weight, not only the fluidity is deteriorated, but also the strength developability may be deteriorated.

[0023]

DETAILED DESCRIPTION OF THE INVENTION

The contents of the present invention will be described in more detail with reference to specific examples. Examples 1 to 6 and Comparative Examples 1 to 9 (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: Anhydrous Commercial product Lithium carbonate: Commercial product Water reducing agent: Melamine-based dispersant, Commercial product Polymer emulsion: Ethylene-vinyl acetate copolymer resin powder, Commercial product Pigment: Red iron oxide, Commercial product Defoamer: Silicone defoamer Foaming agent, commercial product Thickener: Methylcellulose-based thickening agent, commercial product Aggregate: No. 6 silica sand

(2) Preparation of hydraulic composition and mortar test body As a hydraulic composition component, 100 parts by weight of a hydraulic component having various amounts of constituent components are added to a predetermined amount of a curing rate adjusting agent, a water reducing agent and 100 parts by weight of aggregate and 4 parts by weight of water in addition to polymer emulsion, thickener, defoaming agent and pigment
A mortar specimen was prepared by adding 4 parts by weight and kneading for 3 minutes. Table 1 shows the blending ratio of each component in each example.

(3) Measurement of characteristics of mortar The following measurements were performed on the produced mortar test pieces to evaluate the characteristics of the hydraulic coloring finish material composition. From the viewpoint of practicality as a hydraulically colored finishing material composition having self-leveling property, each measurement item was provided with the acceptance criteria shown in Table 2. Flow value: Measured according to JASS 15M-103. Compressive strength: 4 × 4 × 1 shown in JIS R 5201
Mortar is packed in a 6 mm formwork, and the temperature is 20 ° C and the humidity is 80.
% For 3 hours in air and then demolded, then in air (20 ° C,
A molded body additionally cured for a predetermined period in water (80% humidity) or in water (20 ° C., 80% humidity, and then cured in water at 20 ° C. for one day), JIS R 5
It measured according to the method of 201 description. Rate of change in length: 4 × 4 × shown in JIS R 5201
Mortar is packed in a 16 mm formwork, 20 ° C, humidity 8
After curing in air at 0% for 1 day, the molded body obtained by demolding was measured by the comparator method described in JIS A 1125. Number of drying days: Kneaded mortar was cast on a 300 × 300 mm concrete plate with a thickness of 10 mm, and after curing, surface moisture was measured with a ket moisture meter. The number of days required until the surface water content became 8% or less was defined as the number of drying days. Abrasion loss amount: Kneaded mortar, width 100 mm x length 7
mm formwork with a thickness of 10 mm, 20 ° C, humidity 80
%, The amount of wear loss was measured by a Dever abrasion tester (test conditions: abrasion wheel type H-22 overweight 250 g, rotation speed 2000 times) after curing in air for 7 days in air. Was measured. Surface condition (color unevenness, aggregate separation, presence or absence of air bubbles): Mortar prepared by mixing each component is poured onto a 300 × 300 mm concrete plate with a thickness of 10 mm, and the temperature is 20 ° C. and the humidity is 65.
After curing at 28% for 28 days, color unevenness, aggregate separation (described as separation in Table 2) and the presence or absence of air bubbles were visually observed. Table 2 shows the measurement results of the mortar characteristics. It should be noted that, in any of the examples shown here, generation of white sinter was not observed.

[0026]

[Table 1]

[0027]

[Table 2]

From the results shown in Table 2, the composition having the composition falling within the range of the present invention not only passed the judgment criteria for all the items which the self-leveling material should have, but also showed uneven color and white. It can be seen that it has excellent performance as a coloring finishing material having self-leveling property without the occurrence of sinter. On the other hand, in a composition having a composition outside the scope of the present invention, color unevenness occurs, or it is not possible to clear a plurality of basic criteria required as a self-leveling material without occurrence of color unevenness, It can be seen that it is not suitable as a coloring finish material having a self-leveling property.

[0029]

EFFECTS OF THE INVENTION The hydraulic colored finishing material composition of the present invention not only has sufficient fluidity as a self-leveling material, but can also secure a sufficient fluid holding time even at high temperatures, so that the workability in casting is improved. Is extremely excellent in Furthermore, by selecting a hydraulic component that does not produce white sinter and combining a setting regulator suitable for that component, fast hardening and quick drying are enhanced, pigment segregation due to material separation is prevented, and color unevenness is completely eliminated. Not only is it effective in preventing the separation of aggregates and the formation of bubbles on the surface of the cured product, it has also provided a cured product with an excellent appearance, making it possible for the first time to use the self-leveling material as a coloring finishing material. Moreover, it shortens the work period, for example, enables light walking and work on the day of construction, and has excellent abrasion resistance, dimensional stability, and hardening characteristics such as strength. Providing finishing materials.

[Brief description of drawings]

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

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification FI C04B 7:21 C04B 22:14 A 22:14 22:10 22:10 24:24 Z 24:24 24:30 B 24:30 14:02 A 14:02 24:38 B 24:38 24:42 A 24:42) 111: 62 111: 62 (58) Fields investigated (Int.Cl. ⁷ , DB name) C04B ^7/ 00-28 / 36

Claims (11)

(57) [Claims] 1. A hydraulic component composed of alumina cement, gypsum and blast furnace slag, a coagulation modifier composed of aluminum sulfates and a lithium salt, a polymer emulsion, a water reducing agent, a pigment, a thickener and a defoaming agent. Hydraulic colored finishing material composition. 2. The hydraulically colored finishing material 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 with respect to 100 parts by weight of alumina cement. 3. The lithium salt is one or more selected from lithium carbonate, lithium chloride, lithium sulfate, lithium nitrate, lithium hydroxide, lithium acetate, lithium tartrate, lithium malate, and lithium citrate.
The hydraulic colored finish material composition according to claim 1. 4. The hydraulic coloring finishing material composition according to claim 1, wherein the molar ratio of aluminum sulfate to lithium salt is 1 to 50. 5. The hydraulic coloring according to claim 1, wherein the total amount of the aluminum sulfates and the lithium salt is 0.05 to 5 parts by weight with respect to 100 parts by weight of the hydraulic component. Finishing material composition. 6. The amount of the polymer emulsion is the hydraulic component 1.
The hydraulic coloring finish material composition according to any one of claims 1 to 5, which is 0.5 to 25 parts by weight relative to 00 parts by weight. 7. The hydraulic coloring finish material 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. The hydraulically colored finish material composition according to claim 1, wherein the amount of the pigment is 0.5 to 30 parts by weight relative to 100 parts by weight of the hydraulic component. 9. The addition amount of the thickener and the defoaming agent is the hydraulic component 1
1 part by weight or less and 2 parts by weight per 00 parts by weight
The hydraulic coloring finishing material composition according to any one of claims 1 to 8, which is contained in an amount of not more than 10 parts by weight. 10. A hydraulic component consisting of alumina cement, gypsum and blast furnace slag, the proportion of which is 25-120 parts by weight of gypsum and 15-400 parts by weight of blast furnace slag, aluminum sulfate and a particle size of 5 with respect to 100 parts by weight of alumina cement.
The total amount of aluminum sulfate 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. Some coagulation regulators, 0.5 to 100 parts by weight of each hydraulic component
25 parts by weight of polymer emulsion, 0.1 to 5 parts by weight of water reducing agent, 0.5 to 30 parts by weight of pigment, 1 part by weight or less of thickening agent, and 2 parts by weight or less of antifoaming agent Hydraulic colored finishing material composition. 11. A mortar or concrete obtained by further adding an aggregate and water to the hydraulic colored finish material composition according to any one of claims 1 to 10.