JPH07242475A - Method for manufacturing colored cement concrete products - Google Patents

Abstract

(57) [Abstract] [Purpose] The present invention promotes coloring without defective coloring,
The present invention relates to a method for efficiently producing a colored cement concrete product which is capable of forming a strong colored film having a stable color tone at an early stage and which is also excellent in weather resistance and stability and which can prevent the white sinter phenomenon. The present invention is characterized in that the surface of a cement concrete product is treated with an alkali before and / or after the formation of a colored film containing a metal sulfate and / or a reaction product thereof as a main component. The present invention relates to a method for producing a colored cement concrete product.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a colored cement concrete product using a metal sulfate. More specifically, the present invention chemically treats the surface of mortar and / or concrete products such as cement mortar, concrete panel, block, pile, tile, cement concrete building, and construction to accelerate color development. The present invention relates to a method for easily and efficiently producing a colored cement concrete product which does not peel off the formed colored film (layer) and has excellent long-term weather resistance and stability.

[0002]

2. Description of the Related Art Cement concrete products are used in large amounts in the fields of construction and civil engineering, but in recent years, due to harmony with nature and growing interest in the landscape, environmentally friendly colored cement concrete products. Has become strongly desired.

Conventionally, as a method for producing a colored cement concrete product, a pigment is mixed with a raw material such as cement at the time of producing the product, and a paint of a predetermined color or an emulsion of the pigment is brushed on the surface of the product. A method of applying by applying or spraying is known. However, the method of mixing with the above-mentioned raw materials not only requires a large amount of pigment, but also has a drawback that the coloring effect cannot be obtained unless expensive white cement is used, and it is difficult to produce a natural hue. Further, in the case of applying the coating material, peeling of the coating film easily occurs, weather resistance is inferior, etc., and since a large amount of organic solvent is used, there is a problem in handling and safety and hygiene. Is difficult to produce a natural color.

In addition to the method described above, JP-A-4
Japanese Unexamined Patent Publication No. 8-68620 describes a method of applying color to the surface of a cement product by applying an aqueous solution of a metal sulfate such as manganese sulfate or iron sulfate to develop and color the product. Since this method uses a chemical reaction, the drawbacks of the method can be improved, but it takes a long time for the color tone to stabilize due to changes in color over time, In particular, a cement concrete product which has passed a long time after the production does not develop color, or the color development is insufficient and thus cannot be colored, and there is room for improvement in this method.

According to the research conducted by the present inventors, the details of the coloring and coloring mechanism of the method using the metal sulfate are not clear, but free Ca produced by the hydration reaction of cement in the cement concrete product is not clear. (OH) ₂ reacts with a metal sulfate to form fine crystals of a metal hydroxide and develops color,
Along with calcium sulfate and other reaction products that are produced at the same time, they enter into the minute gaps of the cement concrete in the surface layer of the cement concrete product to densify the surface layer, and the surface of the cement concrete is peculiar to the salt of microcrystalline hydroxide. It is presumed that a colored film layer is formed and colored. Further, it takes a long time for the color tone to stabilize, depending on the leaching rate of free Ca (OH) ₂ leaching from the cement concrete product to the surface layer and the reaction rate of hydroxide formation. Therefore, this is the reason why the coloration gradually progresses, and the surface of the cement concrete product that has passed a long time after the production is neutralized or is too dry, so that the exudation of free Ca (OH) ₂ occurs. It is presumed that insufficient coloring causes no coloring or defective coloring.

[0006]

In view of the above-mentioned points, the present inventors have aimed to develop a method for producing a colored cement concrete product capable of improving the above-mentioned problems.
Further, intensive studies were conducted for the purpose of improving the poor color development and instability of color tone in the method using the metal sulfate. As a result, when the surface of the cement concrete product or the surface of the colored film (layer) is treated with an alkali before and / or after the colored film (layer) is formed on the cement concrete product, color development is promoted, A colored film (layer) with a stable color tone can be formed by promoting the formation of a strong colored film (layer) at an early stage, and the film does not peel off and is colored with excellent long-term weather resistance and stability. Cement concrete products can be easily and efficiently manufactured, and even if cement concrete products that have passed a long period of time and have become uncolorable or poorly colored due to neutralization, drying, etc., good coloring The present invention has been made based on the finding that it is possible to prevent the phenomenon of white sinter of cement concrete products, and that the above object can be achieved.

[0007]

According to the present invention, the surface of a cement concrete product is treated with an alkali before and / or after the formation of a colored film containing a metal sulfate and / or a reaction product thereof as a main component. The present invention relates to a method for producing a colored cement concrete product characterized by: Further, the present invention provides a cement concrete product, wherein the periodic table 1B group, 6
Before and / or formation of a colored film containing a metal sulfate and / or a reaction product thereof as a main component by impregnating and / or coating an aqueous solution of a metal sulfate selected from the group consisting of B, 7B and 8 The present invention also relates to a method for producing a colored cement concrete product, characterized in that the surface of the cement concrete product is treated with an alkaline aqueous solution. Furthermore, the present invention provides a cement concrete product for group 1B, 6B.
Before and / or to form a colored film containing a metal sulfate and / or a reaction product thereof as a main component by impregnating and / or coating an aqueous solution of a metal sulfate selected from the group consisting of Group 7, 7B and 8 After that, the present invention relates to a method for producing a colored cement concrete product, which comprises treating the surface of the cement concrete product with an alkaline aqueous solution having a pH of 8 or more.

The cement concrete product to which the present invention can be applied is not particularly limited in kind, shape, size, etc., and examples thereof include cement mortar, concrete panel,
Block, pile, tile, joint, cement concrete
As long as it is a cement mortar product such as a building or a structure, or a cement concrete product, it can be applied to any or any place. Further, the production of the colored cement concrete product according to the present invention may be carried out either at the coloring site or in the cement concrete product manufacturing plant.

In the present invention, the metal sulfate is a water-soluble metal sulfate, preferably 1B group, 6B group of the periodic table.
Water soluble metal sulphates selected from the group consisting of Group 7, Group 7B and Group 8 are used. Specific examples of the metal sulfates include water-soluble metal sulfates such as copper sulfate, chromium sulfate, manganese sulfate, iron sulfate, cobalt sulfate and nickel sulfate. The metal sulfates may be used alone or in combination of two or more.

The metal sulfate is impregnated and / or applied to the surface of the cement concrete product as a solution, generally as an aqueous solution. When impregnated and / or applied, a color is developed to form a colored film on the surface of the cement concrete product. The method of impregnation and / or coating is not particularly limited, but a method such as brush coating, spraying, dipping or the like is usually adopted. The operation of impregnation and / or coating may be performed once or repeatedly. Further, the kind of metal sulfate may be partially changed and impregnated and / or applied. Various colored patterns can be formed by these operations.

The concentration when used as an aqueous solution of metal sulfate varies depending on the amount of metal sulfate impregnated into the cement concrete product and the coating amount, but is in the range of 2% by weight (anhydrous basis) to a saturated concentration or less. , Preferably 5 to 30
It is appropriately selected and used from the range of weight% in consideration of color tone.
Generally, the lower the density, the darker the color tone, and the darker the color tone, but when the concentration is less than 2% by weight, almost no coloration occurs. The amount of the metal sulfate impregnated into the cement concrete product and the coating amount vary depending on the surface condition of the cement concrete product, the type of the metal sulfate, the concentration of the metal sulfate aqueous solution, etc. Product surface area 1
^{1 to} 150 g, preferably 20 to 100 g per m ² is suitable. If the amount of impregnation or coating is too small, coloring is not sufficient, and if it is excessively increased, there is no particular change in color tone.

Further, in the present invention, a cement concrete
It is presumed that the whitening phenomenon of the product can also be suppressed because the alkali content in the product is prevented from being eluted from the inside to the surface by the densified surface layer and the colored film.

In the present invention, the alkali treatment may be carried out before or after the formation of the colored film containing the metal sulfate and / or the reaction product thereof as the main component in the cement concrete product. You may go later. However, it is more effective to accelerate the color development even for a cement concrete product whose surface is neutralized or is too dry by performing it before the formation of the colored film, so that the color tone is stable and strong. Not only can a colored film be formed at an early stage, but also a cement concrete for a metal sulfate aqueous solution can be obtained.
It is preferable because the amount of impregnation and / or application is small because the product is not easily sucked into the product.

The alkali treatment is generally a method of impregnating and / or applying an alkaline aqueous solution having a pH of 8 or more, preferably a pH of 10 or more onto the surface of the cement concrete product before and / or after the formation of the colored film. Done. If the pH is lower than 8, there is almost no color-promoting effect, so it is preferable to use an alkaline aqueous solution having a high PH. The method of impregnation and / or coating is not particularly limited, but, for example, methods such as brush coating, spraying, and depping are usually adopted. The operation of impregnation and / or coating may be performed once or repeatedly.

The amount of the impregnated and / or applied alkaline aqueous solution is
Although it varies depending on the surface condition of the cement concrete product, the pH of the alkaline aqueous solution, the viscosity, the drying speed, etc., ^{20 to} 2000 g, preferably 50 to 500 g is suitable per 1 m ^{2 of} the product surface area to be treated. If the amount of impregnation and / or coating is too small, the effect cannot be expected, and if it is too large, the metal sulfate component cannot penetrate into the cement concrete product, which is not preferable.

When the alkali treatment is carried out before the formation of the colored film, it is suitable for early color development to carry out the above-mentioned coloring operation with a metal sulfate while the alkali-treated surface layer is in a wet state.

The alkaline substance used for the alkali treatment may be any one that is water-soluble and has a pH of the aqueous solution of 8 or more, preferably 10 or more, and the alkaline substance may be completely dissolved in water before use. It may be a partially dissolved suspension aqueous solution. Specific examples of the alkaline substance include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, sodium bicarbonate (bi) carbonate, (bi) carbonates of alkali metals such as (bi) potassium carbonate, and sodium metasilicate. , Silicates of alkali metals such as potassium metasilicate, hydroxides of alkaline earth metals such as water glass, calcium hydroxide, magnesium hydroxide and strontium hydroxide, oxidation of alkaline earth metals such as calcium oxide and magnesium oxide The thing etc. can be mentioned. Moreover, these may be a mixture. Sludge and sludge water discharged from the cement concrete factory can also be used.
Among the alkaline substances, calcium oxide, calcium hydroxide and the like are one of the components of the cement concrete product and are therefore particularly preferably used.

In the present invention, the mechanism by which the color development is promoted by the alkali treatment and a strong colored film (layer) having a stable color tone can be formed in an early stage is not fully clarified. The surface (layer) of the cement product is activated to accelerate the reaction with the metal sulfate, and the alkali more firmly integrates the surface (layer) of the cement concrete product with the metal sulfate and its reaction product. It is presumed that it has an effect.

[0019]

EFFECTS OF THE INVENTION According to the present invention, there is no color failure and color development is promoted, the formation of a strong colored film layer can be promoted at an early stage, and a colored film having a stable color tone can be formed. It is possible to easily and efficiently produce a colored cement concrete product which is excellent in long-term weather resistance and stability without being worn out, and also to prevent the whitening phenomenon of the cement concrete product.

[0020]

[Examples] In each example, the accelerated weathering test is conducted according to JIS
According to A1415 "Method of accelerated exposure test for plastic building materials", length 150 mm, width 70 mm, thickness 20
Using a 0 mm sample, the test was carried out under the conditions of a sunshine carbon, a black panel temperature of 63 ± 3 ° C., a humidity of 50% RH, and a spray cycle of 12 minutes in 60 minutes.

Example 1 In a 30 × 30 × 3 cm mold, ordinary Portland cement: sand = 1: 2 (weight ratio), water cement ratio (W / C) =
Pour 0.45 (weight ratio) of cement mortar, cure overnight in moist air, then demold, then overnight moist air, then 9
Cement panels were manufactured by performing air curing for 0 days. 1 aqueous solution of PH12 sodium hydroxide on the cement panel
00 g / m ^{2 was} applied, and while the panel surface was wet, 80 g / m ^{2 of an} iron sulfate aqueous solution having a concentration of 15 wt% was spray-impregnated and left at room temperature. The surface of the cement panel was colored at the same time as it was dried, and a yellowish brown colored film was formed on the surface 1 hour after the impregnation treatment. After the panel was left at room temperature and dried for 1 hour, a colored cement panel with a dark tan coating comparable to accelerated weathering of 500 hours was obtained. The colored cement panel had a stable dark yellow-brown color tone even when left outdoors for one year or more, and no fading or white flower phenomenon was observed.

Example 2 The same sodium hydroxide aqueous solution and iron sulfate aqueous solution as in Example 1 was used, except that the air curing for 90 days in the production of the cement panel of Example 1 was changed to 180 days. A colored cement panel having a film of was obtained. The results were excellent as in Example 1.

Comparative Example 1 An attempt was made to manufacture a colored cement panel in the same manner as in Example 1 except that the aqueous sodium hydroxide solution of Example 1 was not applied. A thin yellowish brown film was formed on the panel surface as the sprayed iron sulfate aqueous solution was dried.
It did not reach a dark tan color comparable to 00 hours. After that, when it was left outdoors, the color tone gradually turned brown and changed to dark yellow-brown over half a year to one year.

COMPARATIVE EXAMPLE 2 The example of Example 1 was repeated except that the air curing for 90 days in the production of the cement panel of Example 1 was changed to 180 days, and the aqueous sodium hydroxide solution of Example 1 was not applied. An attempt was made to produce a colored cement panel in the same manner as in 1.
However, the sprayed iron sulfate aqueous solution penetrated the panel and did not develop color. Then, when the operation of spraying 80 g / m ^{2 of} iron sulfate aqueous solution having a concentration of 15 wt% again was repeated twice, the panel only slightly changed to yellow.

Example 3 A cement panel was used in which the air curing for 90 days in the production of the cement panel of Example 1 was changed to 180 days.
100g of H12 calcium oxide aqueous solution (lime water)
/ M ² applied and the density is 20 while the panel surface is wet.
A weight% manganese sulfate aqueous solution was spray-impregnated at 80 g / m ² and left to stand at room temperature. The surface of the cement panel was colored simultaneously with drying, and a brown colored film was formed on the surface 1 hour after the impregnation treatment. After the panel was left at room temperature and dried for 1 hour, a colored cement panel having a brown film comparable to accelerated weathering for 500 hours was obtained. This colored cement panel had a stable brown color tone even when it was left outdoors for one year or longer, and no fading or white flower phenomenon was observed.

Comparative Example 3 An attempt was made to produce a colored cement panel in the same manner as in Example 3 except that the lime water of Example 3 was not applied. However, the sprayed manganese sulfate aqueous solution penetrated the panel and did not develop color. Then, the operation of spraying an aqueous solution of manganese sulfate having a concentration of 20% by weight again at 80 g / m ² was repeated twice, but no color was developed.

Example 4 A cement panel obtained by replacing the air curing for 90 days in the production of the cement panel of Example 1 with 180 days was used.
Apply 100g / m ^{2 of} H12 cement sludge water,
While the surface of the panel was wet, an aqueous solution of chromium sulfate having a concentration of 12% by weight was sprayed and impregnated at 80 g / m ² . The surface of the cement panel was colored simultaneously with drying, and a blue-green colored film was formed on the surface 1 hour after the impregnation treatment. After the panel was left at room temperature and dried for 1 hour, a colored cement panel having a blue-green film equivalent to accelerated weathering of 500 hours was obtained. This colored cement panel had a stable blue-green color tone even when it was left outdoors for one year or more, and no fading or white flower phenomenon was observed.

Comparative Example 4 An attempt was made to produce a colored cement panel in the same manner as in Example 4 except that the cement sludge water of Example 4 was not applied. However, the sprayed chromium sulfate aqueous solution penetrated the panel and did not develop color. So again concentration 12
When the operation of spraying 80 wt / m ^{2 of a} wt% chromium sulfate aqueous solution was repeated twice, the panel only slightly changed to blue-green.

Example 5 Using a cement panel in which the air curing for 90 days in the production of the cement panel of Example 1 was changed to 180 days, P
An aqueous solution of H12 water glass was applied at 100 g / m ^2, and while the surface of the panel was wet, a copper sulfate aqueous solution having a concentration of 12% by weight was sprayed and impregnated at 80 g / m ² and left at room temperature. The surface of the cement panel was colored simultaneously with drying, and a blue-green colored film was formed on the surface 1 hour after the impregnation treatment. After the panel was left at room temperature and dried for 1 hour, a colored cement panel having a blue film comparable to accelerated weathering for 500 hours was obtained. This colored cement panel had a stable blue color tone even after being left outdoors for one year or more, and no fading or white flower phenomenon was observed.

Comparative Example 5 Except that the aqueous solution of water glass of Example 5 was not applied,
An attempt was made to manufacture a colored cement panel in the same manner as in Example 5. However, the sprayed copper sulfate aqueous solution penetrated into the panel and did not develop color. Then, when the operation of spraying a copper sulfate aqueous solution having a concentration of 12% by weight again at 80 g / m ² was repeated twice, the panel only slightly turned blue.

Example 6 A cement panel obtained by replacing the 90-day air curing in the production of the cement panel of Example 1 with 180 days was used, and 160 g / m ^{2 of a} 20 wt% concentration manganese sulfate aqueous solution was applied to the panel. While the surface was wet, a sodium hydroxide aqueous solution of PH12 was sprayed to impregnate it at 50 g / m ² and allowed to stand at room temperature. The surface of the cement panel was colored simultaneously with drying, and a brown colored film was formed on the surface 1 hour after the impregnation treatment. Leave the panel at room temperature for 1 hour to dry, and then accelerate
A pigmented cement panel with a brown coating comparable to 00 hours was obtained. This colored cement panel had a stable brown color tone even when it was left outdoors for one year or longer, and no fading or white flower phenomenon was observed.

Comparative Example 6 An attempt was made to produce a colored cement panel in the same manner as in Example 6 except that the aqueous sodium hydroxide solution of Example 6 was not applied. As the sprayed aqueous solution of manganese sulfate was dried, a thin brown film was formed on the panel surface, but the brown color comparable to accelerated weathering of 500 hours was not reached. When it was left outdoors thereafter, the color gradually changed to brown and changed to brown over a period of half a year to one year.

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[Procedure amendment]

[Submission date] March 14, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 2

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

[0007]

According to the present invention, the surface of a cement concrete product is treated with an alkali before and / or after the formation of a colored film containing a metal sulfate and / or a reaction product thereof as a main component. The present invention relates to a method for producing a colored cement concrete product characterized by: Further, the present invention provides a cement concrete product, wherein the periodic table 1B group, 6
Before and / or before forming and / or applying an aqueous solution of a metal sulfate selected from the group consisting of Group A, Group 7A and Group 8 to impregnate and / or coat a metal sulfate and / or a reaction product thereof. The present invention also relates to a method for producing a colored cement concrete product, characterized in that the surface of the cement concrete product is treated with an alkaline aqueous solution. Furthermore, the present invention provides a cement concrete product for the group 1B, 6A.
Before and / or to form a colored film containing a metal sulfate and / or a reaction product thereof as a main component by impregnating and / or applying an aqueous solution of a metal sulfate selected from the group consisting of Group 7, Group 7A and Group 8 After that, the present invention relates to a method for producing a colored cement concrete product, which comprises treating the surface of the cement concrete product with an alkaline aqueous solution having a pH of 8 or more.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

In the present invention, the metal sulfate is a water-soluble metal sulfate, preferably Group 1B, 6A of the periodic table.
Water soluble metal sulphates selected from the group consisting of Group 7, Group 7A and Group 8 are used. Specific examples of the metal sulfates include water-soluble metal sulfates such as copper sulfate, chromium sulfate, manganese sulfate, iron sulfate, cobalt sulfate and nickel sulfate. The metal sulfates may be used alone or in combination of two or more.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

[0019]

EFFECTS OF THE INVENTION According to the present invention, color development is promoted without defective coloring, and a colored film having a stable color tone can be formed by promptly forming a strong colored film layer, resulting in peeling of the film. Without doing so, it is possible to easily and efficiently produce a colored cement concrete product excellent in long-term weather resistance and stability, and further prevent the whitening phenomenon of the cement concrete product.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

Comparative Example 1 An attempt was made to produce a colored cement panel in the same manner as in Example 1 except that the aqueous sodium hydroxide solution of Example 1 was not applied. A thin yellowish brown film was formed on the panel surface as the sprayed iron sulfate aqueous solution was dried.
It did not reach a dark tan color comparable to 00 hours. After that, when it was left outdoors, the color tone gradually turned brown and changed to dark yellow-brown over half a year to one year.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

COMPARATIVE EXAMPLE 2 The example of Example 1 was repeated except that the air curing for 90 days in the production of the cement panel of Example 1 was changed to 180 days, and the aqueous sodium hydroxide solution of Example 1 was not applied. An attempt was made to produce a colored cement panel in the same manner as in 1.
However, the sprayed iron sulfate aqueous solution penetrated the panel and did not develop color. Then, when the operation of spraying 80 g / m ^{2 of} iron sulfate aqueous solution having a concentration of 15 wt% again was repeated twice, the panel only slightly changed to yellow.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

Comparative Example 3 An attempt was made to produce a colored cement panel in the same manner as in Example 3 except that the lime water of Example 3 was not applied. However, the sprayed manganese sulfate aqueous solution penetrated the panel and did not develop color. Then, the operation of spraying an aqueous solution of manganese sulfate having a concentration of 20% by weight again at 80 g / m ² was repeated twice, but no color was developed.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

Comparative Example 4 An attempt was made to produce a colored cement panel in the same manner as in Example 4 except that the cement sludge water of Example 4 was not applied. However, the sprayed chromium sulfate aqueous solution penetrated the panel and did not develop color. So again concentration 12
When the operation of spraying 80 wt / m ^{2 of a} wt% chromium sulfate aqueous solution was repeated twice, the panel only slightly changed to blue-green.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

Comparative Example 5 Except that the aqueous solution of water glass of Example 5 was not applied,
An attempt was made to produce a colored cement panel in the same manner as in Example 5. However, the sprayed copper sulfate aqueous solution penetrated into the panel and did not develop color. Then, when the operation of spraying a copper sulfate aqueous solution having a concentration of 12% by weight again at 80 g / m ² was repeated twice, the panel only slightly turned blue.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

Comparative Example 6 An attempt was made to produce a colored cement panel in the same manner as in Example 6 except that the aqueous sodium hydroxide solution of Example 6 was not applied. As the sprayed aqueous solution of manganese sulfate was dried, a thin brown film was formed on the panel surface, but the brown color comparable to accelerated weathering of 500 hours was not reached. When it was left outdoors thereafter, the color gradually changed to brown and changed to brown over a period of half a year to one year.

Claims (3)

[Claims] 1. A colored cement characterized in that the surface of the cement concrete product is treated with an alkali before and / or after forming a colored film containing a metal sulfate and / or a reaction product thereof as a main component. Manufacturing method of concrete products. 2. A cement concrete product with a periodic table 1
Before impregnating and / or coating an aqueous solution of a metal sulfate selected from the group consisting of B, 6B, 7B and 8 to form a colored film containing the metal sulfate and / or its reaction product as a main component. And / or the cement concrete after being generated
A method for producing a colored cement concrete product, which comprises treating the surface of the product with an alkaline aqueous solution. 3. The method for producing a colored cement concrete product according to claim 2, wherein the pH of the alkaline aqueous solution is 8 or more.