JPH101378A - Method for coloring inorganic building material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily produce patterns having unequal colors on inorg. building material surfaces by impregnating these building material surfaces with specific compds., then impregnating the surfaces with oxide, thereby forming colored protective layers on the building material surfaces. SOLUTION: The surfaces of the inorg. building materials which are, for example, calcium silicate boards, slate boards, concrete mortar boards, asbestos boards, plaster, gypsum boards, etc., are preferably impregnated with the water- soluble metal chlorides (e.g.; iron chloride, copper chloride, manganese chloride, cobalt chloride, nickel chloride, chromium chloride, etc.) selected from group 1B, 6B, 7B or 8B of periodic table and thereafter the surfaces are impregnated with an oxidizing agent (e.g.: hydrogen peroxide water), by which the colored protective layers are formed on the building material surfaces. The surfaces of the inorg. building materials are impregnated with the oxidizing agent and thereafter, the surfaces are impregnated with the inorg. chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of coloring an inorganic building material by coloring the surface of the inorganic building material by utilizing a chemical reaction.

[0002]

2. Description of the Related Art A method of coloring a surface of an inorganic building material by using a chemical reaction has been disclosed in Japanese Patent Application Laid-Open No. 52-6942.
No. 8 discloses a method in which an aqueous solution of a metal salt is applied to the surface of concrete, dried, baked, and then the surface is washed with water to fix and color the colored metal oxide or oxy compound.

In Japanese Patent Application Laid-Open No. Hei 7-247186, an oxidizing agent is added to a metal sulfate and applied to the concrete surface, or a metal sulfate is applied to the concrete surface to form a colored film. A coloring method is disclosed in which an oxidizing agent is applied and treated after or before the formation of a colored film to promote the color development accompanying the oxidation of the metal sulfate.

[0004]

However, the above method of firing a concrete surface impregnated with an aqueous solution of a metal salt has a problem in that the use of fire is restricted at construction work sites. On the other hand, in the method of applying and permeating a metal salt aqueous solution to the concrete surface, it takes a long time to fix the color on the concrete surface because the use of the aqueous solution for a highly water-absorbing building material takes a long time to dry. There was a problem in workability and economy. Also,
The colors and patterns required for building flooring materials and the like have been increasingly diversified, and in particular, recently, demand for patterns with uneven color has increased due to the natural texture.

Accordingly, the present invention provides a method of coloring an inorganic building material by utilizing a chemical reaction, whereby a pattern having uneven color can be made to appear, and the simplicity and economy of construction can be improved. A new method for coloring inorganic building materials will be provided.

[0006]

[Means for Solving the Problems] To solve such problems,
After impregnating the surface of the inorganic building material with the metal chloride, the present invention impregnates the surface with an oxidizing agent, or impregnating the surface of the inorganic building material with the oxidizing agent, and then impregnating the surface with the metal chloride. Provided is a method for coloring an inorganic building material, wherein a coloring protective layer is formed on the surface of the building material by impregnation.

According to the present invention, the metal chloride reacts with the oxidizing agent on the surface of the inorganic building material, and not only the color and color unevenness characteristic of the oxidation reaction of the metal chloride can appear on the surface of the building material, It is possible to reduce the water absorption and the efflorescence phenomenon on the surface of the building material, and it is also possible to improve the long-term weather resistance, stability and abrasion resistance.

The inorganic building material in the present invention is required to be an inorganic building material whose surface layer can be impregnated with a liquid, for example, it has a porous shape. If this condition is satisfied, for example, a calcium silicate board, a straight board, Concrete mortar boards, asbestos boards, plasters, gypsum boards and the like are not limited. Since the metal chloride itself has low adhesion and film forming ability, it is impregnated as a chloride solution on the surface of the building material and reacted with a substance in the building material component and an oxidizing agent to fix it on the surface of the building material as an insoluble substance. From
Inorganic building materials such as glassy, porcelain, stone, etc., which have no room for liquid impregnation, are not suitable for the present invention.

The metal chloride in the present invention includes a water-soluble metal chloride, preferably a group 1B, 6B or 7B of the periodic table.
A water-soluble metal chloride selected from Group 8B or Group 8B can be used. Specifically, it is a metal chloride such as iron chloride, copper chloride, manganese chloride, cobalt chloride, nickel chloride, and chromium chloride. In addition, two or more kinds of metal chlorides can be used as a mixture, and in that case, a color peculiar to each metal chloride can be prepared, and the coloring variation can be further expanded.

[0010] In order to impregnate the building material surface with the metal chloride, the metal chloride can be dissolved in water, and the aqueous solution can be applied or sprayed by brushing, spraying, dipping, or the like. It is preferable to dissolve the metal chloride in a mixed solution of alcohol and water (hereinafter, referred to as alcohol water), and apply or spray this solution on the surface of the building material. Metal chlorides have the property of being easily dissolved in alcoholic water.Moreover, when impregnating building materials as an aqueous alcoholic solution, the metal chloride retains strength such as abrasion resistance compared to when it is applied as an aqueous solution. , Since the drying time can be extremely short,
Workability can be significantly improved.

Further, alcoholic water in which metal chlorides are dissolved has an alcohol concentration of about 5 to about 30%, particularly about 10%.
Preferably, it is about 30%. Up to 30% concentration, the alcohol concentration increases and the drying time decreases.
If the content exceeds 0%, some substances become gel-like, and on the contrary, the drying time may be prolonged. In addition, the metal chloride can be dissolved in 100% alcohol and the alcohol solution can be impregnated on the surface of the building material. In this case, however, the drying time is further shortened, but the risk of burning due to ignition increases. The above-mentioned alcoholic water is preferred.

When the metal chloride is dissolved in water or alcoholic water, the concentration of the metal chloride is preferably about 5 to about 20% by weight, though it depends on the amount of the coating. If the amount is significantly lower than 5% by weight, the color may be extremely light. If the amount is significantly higher than 20% by weight, there is no tendency for the color to be darkened.

The amount of the metal chloride impregnated on the surface of the building material varies depending on the surface condition of the inorganic building material, the type of the metal chloride, and the concentration of the metal chloride.
Preferably, it is about 100 g to about 800 g per ² pieces.
If the amount is significantly less than 100 g / m ² , color development may not be sufficient, and if the amount is significantly more than 800 g / m ² , no change in color development is observed, which is economically undesirable.

Next, the oxidizing agent used in the present invention is a solid,
Any liquid may be used, but those having water solubility are preferred. For example, chlorates such as sodium chlorite, peroxides such as calcium peroxide and hydrogen peroxide, sodium nitrite, bleached powder and the like can be suitably used. These oxidizing agents may be applied and impregnated on the surface of the building material as an aqueous solution or the like. In this case, the concentration varies depending on the amount to be applied. For example, in the case of hydrogen peroxide, the concentration is preferably about 3 to 10% by weight. If the concentration is significantly lower than 3% by weight, the oxidizing ability may not be exhibited. If the concentration is significantly higher than 10% by weight, there is no particular difference in the oxidation effect.

The amount of the oxidizing agent impregnated on the surface of the building material is as follows:
The surface area of the inorganic building material varies depending on the surface condition of the inorganic building material, the type of metal chloride, and the concentration of the metal chloride solution.
About 100 g to about 800 g per m ² is preferred. 100
If the amount is significantly less than g / m ² , the oxidation effect cannot be expected, and if it is significantly more than 800 g / m ^2, no difference in the effect occurs, which is economically undesirable. Further, the impregnation with the oxidizing agent may be performed not only once but also several times while observing the degree of color development.

In the present invention, when the oxidizing agent is impregnated after the impregnation with the metal chloride, it is preferable that the oxidizing agent solution is impregnated after the metal chloride solution is dried. By doing so, the oxidizing agent can be impregnated in a shorter time, and the workability can be further improved. On the other hand, when impregnating with a metal chloride after impregnating with an oxidizing agent, there is a tendency that a better coloring effect can be obtained when the oxidizing agent is still in a wet state.

In the present invention, the number of times the metal chloride is impregnated on the surface of the building material may be not only one time but also several times. Alternatively, after one kind of metal chloride is applied first, another kind of metal chloride is impregnated. May be impregnated.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below while considering the results of various tests.

(Coloring test when the type of metal chloride is changed) Ferrous chloride, ferric chloride, cuprous chloride, cobalt chloride and manganese chloride are dissolved in water, and 5% by weight. The concentration was adjusted. On the other hand, the specimen was cement mortar board A (the following: cement mortar (cement: sand = 1: 2, water-cement ratio: 40%)) cured in a test room at 20 ° C. and 65% humidity until the age of 28 days. The same applies to each test.). In this test, 300 g / m ² of each metal chloride aqueous solution was applied and impregnated on the surface of the cement mortar plate A, and after drying, 300 g / m ² of a 3% by weight aqueous hydrogen peroxide solution as an oxidizing agent was applied and impregnated. The observation was performed by observing the state of the surface of the building material, and the object not coated with the oxidizing agent was used as a non-treated material. The results are shown in Table 1 below.

[0020]

[Table 1]

From the above, it was found that the treatment with the oxidizing agent deepened the color of any of the specimens, and gave a natural texture peculiar to the oxide of metal chloride.

(Color development test when the concentration of the metal chloride solution is changed) Three kinds of inorganic building materials, ie, a calcium silicate plate, a straight plate, and a cement mortar plate A, are prepared. 3, 5, 10, 15, 2 respectively
A ferric chloride aqueous solution prepared to each concentration of 0, 25, 30, 35, 40, 45, and 50% by weight is applied and impregnated with 700 g / m ^2, and after drying, a 10% by weight aqueous hydrogen peroxide solution is used as an oxidizing agent. Was applied and impregnated at 700 g / m ^{2, and} the coloring of the surface of the building material was observed thereafter.

As a result, with respect to any of the inorganic building materials, when the concentration of ferric chloride was 3% by weight, the color did not sufficiently develop.
At 5% by weight or more, sufficient coloring was confirmed for all inorganic building materials. Also, even if it is more than 20% by weight,
Since no tendency to increase color development was observed, it is considered that the concentration of the metal chloride solution is preferably about 5 to about 20% by weight.

(Coloring test when the concentration of the oxidizing agent solution was changed) A hydrogen peroxide solution having a concentration adjusted to 3, 10, 15, 20, 25, or 30% by weight was prepared. In this test, a 20% by weight aqueous solution of cobalt chloride was applied at 500 g / m ² to the surface of the cement mortar board A, and before forming a colored film, 3 to 30% by weight of aqueous hydrogen peroxide was added at 400 g / m ^2. m ^{2 was} applied and impregnated, and the color development on the surface of the cement mortar plate A was observed.

As a result, no difference was observed in the coloring properties depending on the concentration of the hydrogen peroxide solution.

(Abrasion test) According to JIS-K-7204, 500 rotations and 10 rotations using a Taber type abrasion tester.
The wear resistance of the cement mortar board to which the present invention was applied was tested by measuring the wear thickness at the end of 00 rotation.

In the test specimen of this test, a 15% aqueous solution of ferrous chloride having a concentration of 20% by weight was applied to the surface of the cement mortar plate A.
0 g / m ² coated and impregnated, dried and impregnated with 150 g / m ^{2 of a} 5% by weight aqueous hydrogen peroxide solution, and then sufficiently dried. iron aqueous ethanol (water: ethanol = 80: 20) was 150 g / m ² coating impregnation, dried 5% strength by weight aqueous hydrogen peroxide 150 g / m ² is coated impregnated in, which was then sufficiently dried, cement mortar A 20% by weight aqueous solution of aqueous ferrous chloride methanol (water: methanol = 80: 20) was applied to the surface of the plate A at 150 g / m ^2.
5% by weight of hydrogen peroxide solution 15
The coating was impregnated with 0 g / m ² and then sufficiently dried.

As a comparative example, an untreated cement mortar plate A was similarly tested. The results are shown in Table 2 below and FIG.

[0029]

[Table 2]

As a result, the wear thickness of the cement mortar board A impregnated with ferrous chloride was remarkably smaller than that of the untreated cement mortar plate A, and the wear resistance was excellent.

(Colorability test for already colored building material surface) A 20% by weight concentration of ferric chloride at a concentration of 20% by weight was applied to the floor surface on which a concrete surface colored flooring material (manufactured by ABC Shokai Co., Ltd., trade name: Karakrete, Design Cleat) was applied. 300 g / m of aqueous solution
⁽²⁾ Impregnation, before the ferric chloride forms a colored film, 300 g / vol.
m ^{2 was} applied and impregnated, and the color of the floor material surface was observed. As a result, the surface of the flooring material became deeper in color due to a synergistic effect with the conventional color tone, and became more natural in color.

Further, the above-mentioned aqueous solution of ferric chloride was applied and impregnated, and after forming a colored film, 300 g / m ² of a 3% by weight aqueous solution of hydrogen peroxide was applied and impregnated. The same result as when water was applied was obtained.

(Weather Resistance Test) According to JIS-A-1415 (a method of accelerated exposure test for plastic building materials), a specimen having a length of 150 m ² , a width of 70 m ² , and a thickness of 15 m ² was prepared. Black panel temperature 63 ±
3 ° C, humidity 50% RH, spray cycle 1 in 120 minutes
The weather resistance test was performed under the conditions of 8 minutes.

In the test specimen of this test, a ferrous chloride aqueous solution having a concentration of 20% by weight was applied to the surface of the cement mortar plate A for 200 hours.
g / m ² , and then impregnated with 400 g / m ^{2 of a} 3% by weight aqueous solution of hydrogen peroxide. Was used.

As a result, the test specimen after 500 hours of accelerated weathering had a stable yellow-brown color tone and no whitening phenomenon was observed.

Next, the surface of the cement mortar plate A was
An aqueous solution obtained by mixing a 1% by weight aqueous solution of ferric chloride at a concentration of 3% by weight and an aqueous solution of hydrogen peroxide at a concentration of 3% by weight was 300 g / m ^{2 2.}
The test was performed under the same conditions as described above. As a result, the color became yellowish brown in the process of mixing the aqueous ferric solution and the aqueous hydrogen peroxide, but the color could be fixed as it was even when sprayed on the surface of the underlying mortar. In addition, the results of the weather resistance test were almost the same as those described above.

(Water Permeability Test) According to JIS-A-6910, water was put into the pipette up to a height of 250 m ² from the surface of the specimen using a water permeability test instrument shown in FIG. The scale of the pipette was read, and the water permeability was measured from the difference in water level before and after the test.

In the test specimen of this test, a 60% aqueous solution of cobalt chloride at a concentration of 20% by weight was applied to the surface of the cement mortar plate A.
0 g / m ² was sprayed and impregnated, and after drying, a hydrogen peroxide solution having a concentration of 3% by weight was further sprayed and impregnated with 600 g / m ² and used after 28 days. Further, as a control, the same test was performed on an untreated cement mortar plate A.
The results are shown in FIG. As a result, when the aqueous solution of cobalt chloride was sprayed and treated with an oxidizing agent, only about one-fifth of the water permeated compared to the untreated ground cement mortar.

(Drying time test when dissolved in alcohol or alcoholic water) Methanol concentration of 0% to 100%
Between 10% and 10 g of ferrous chloride was added to 100 m ^{2 of} each alcohol water.
Was dissolved, 1 cc (1 g) of each solution was dropped on the upper surface of the glass plate, left in a test room at 20 ° C. and a humidity of 65%, and the drying time was measured by measuring the weight one hour later.

As a result, in alcoholic water having a concentration of up to 30%, the alcohol concentration was increased and the drying speed was increased. However, when the concentration was more than 30%, a gel-like tendency was likely to appear. A tendency for thinning was observed.

Next, nickel chloride, which is known to have relatively low solubility in alcohol among metal chlorides, is mixed with methanol or ethanol at the same mixing ratio as described above, and a drying test is performed as described above. went. As a result, when nickel chloride is mixed with ethanol, the mixture becomes a gel from the mixing stage, drying becomes slow and the color density becomes low. On the other hand, when mixed with methanol, the mixing ratio of methanol is good up to 30%. It was confirmed that, after drying, as in the case of the above-mentioned ferrous chloride, if it exceeds 30%, turbidity occurs and separation occurs. Therefore, it was found that when nickel chloride is used among the metal chlorides, methanol is preferably used as the alcohol to be dissolved.

(Coloring test in the case of alkali treatment) The surface of a dried slate plate was impregnated with 300 g / m ² of a 10% by weight aqueous solution of caustic soda, and then 30% by weight.
When an aqueous solution of cuprous chloride having a concentration of 300 g / m ^{2 was} applied and impregnated, a blue color was obtained. Next, 300 g / m ² of a 5% by weight aqueous solution of hydrogen peroxide was applied and impregnated on the surface of the slate plate to obtain a mottled blue and brown color tone. The same effect was obtained by applying a cupric chloride aqueous solution to the dried slate plate and then making it alkaline with caustic soda.

[Brief description of the drawings]

FIG. 1 is a graph showing the results of a wear test.

FIG. 2 is an explanatory view showing a water permeability test device used in a water permeability test.

FIG. 3 is a graph showing the results of a water permeability test.

Claims (3)

[Claims] 1. A method for coloring an inorganic building material, comprising impregnating the surface of an inorganic building material with a metal chloride and then impregnating the surface with an oxidizing agent to form a colored protective layer on the surface of the building material. 2. A method for coloring an inorganic building material, comprising impregnating the surface of an inorganic building material with an oxidizing agent and then impregnating the surface with a metal chloride to form a colored protective layer on the surface of the building material. 3. The coloring of an inorganic building material according to claim 1, wherein the metal chloride is dissolved in a mixture of alcohol and water, and the solution is impregnated on the surface of the inorganic building material. Method.