JP2556304B2 - Inorganic film forming composition - Google Patents

Description

The present invention relates to a composition for forming an inorganic film, and more specifically, by applying a composition obtained by kneading a specific raw material with water onto a building board or a metal in a relatively thick manner at room temperature. The present invention relates to an inorganic cured film which is easily and highly adherently formed, and the film is lightweight and has excellent water resistance, fire resistance and the like.

Heretofore, various inorganic film-forming compositions containing a water-soluble alkali silicate as a main vehicle have been known. The method of use is mainly to mix a water-soluble alkali silicate with a curing agent such as silicofluoride, acidic metal oxide, phosphate, borate, divalent metal sulfate, and divalent metal sulfite. As a binding component, on which various pigments and additives are mixed,
This is applied to a thickness of about several hundreds of microns, and although such a coating film has excellent adhesiveness and nonflammability, it is inherently poor in water resistance and thus has poor practicality.
Further, nothing that improves water resistance and fire resistance was found.

The inventors of the present invention have tackled such a problem for a long time, and as a result of continuing diligent research efforts, as a result, the present invention has been completed by using a composition in which specific components are blended. That is,
BEST MODE FOR CARRYING OUT THE INVENTION The present invention is a water-soluble alkali silicate (hereinafter referred to as "first component"), a carbonate or complex carbonate which is sparingly soluble or insoluble in water and can be decomposed at about 700 ° C or lower (hereinafter referred to as "first component"). ), A water-soluble alkali silicate curing agent (hereinafter referred to as “first component”), a metal-based foaming agent (hereinafter referred to as “first component”), a foaming stabilizer (hereinafter referred to as “first component”), and water (hereinafter referred to as “first component”). Ingredients) is the main raw material.

In the present invention, as the first component, a water-soluble alkali silicate is used, which makes it possible to easily form a film with excellent performances only by mixing it with other raw materials at room temperature for the first time. Even though it is a film, it exhibits effective caking properties and efficiently performs its foaming reaction. The above-mentioned object cannot be achieved with a poorly water-soluble or insoluble alkali silicate such as ordinary anhydrous water glass cullet. Examples of the alkali component that constitutes the fourth component include lithium, sodium, potassium, rubidium, and other alkali metals and quaternary ammonium salts. Particularly, sodium, potassium, and the like are inexpensive and easily available, and Acceleration of the curing effect of the coating is remarkable, which is desirable. The composition of the first component is not limited as long as it is water-soluble, and the molar ratio of the alkaline substance to SiO ₂ is not particularly limited, but the above molar ratio is preferably 1.5 to 4.0, and more preferably about 1.8 to 3.0.

Specific examples of the carbonate, the complex carbonate or the minerals thereof, which is the first component used in the present invention, is sparingly soluble or insoluble in water and capable of decomposing at about 700 ° C. or lower. That is, as the carbonate, beryllium carbonate, magnesium carbonate, manganese carbonate, iron carbonate, zinc carbonate, cadmium carbonate, thallium carbonate, lead carbonate, arsenic carbonate, scandium carbonate, and as the complex carbonate, dolomite, zinc hydroxycarbonate, etc. Further, examples of the carbonate or complex carbonate mineral include hydrozincite, dolomite, redhill stone, and iron rhodochrosite. These first components are
Although it is almost insoluble in water, some of it is very slightly soluble and has the property of generating and decomposing carbon dioxide gas in the temperature range of about 100 to 700 ° C. As a matter of course, some things may be accompanied by the generation of water, but this does not particularly hinder the present invention.
These are used in the form of powder or granules,
The particle size is preferably about 10 to 1000 microns in diameter.

The hardener of the water-soluble alkali silicate as the first component in the present invention is a hydraulic cement, silica dust, a divalent or higher metal salt of a higher fatty acid, a divalent or higher metal salt of a water-soluble polymer having a carboxyl group, an acid. It is at least one selected from the group consisting of metal oxides, phosphates, borates, divalent metal sulfates and divalent metal sulfites. Specific examples of this curable component are as follows. As hydraulic cement, hydraulic lime, natural cement, portland cement, plain cement such as alumina cement, lime mixed cement, blast furnace cement, silica cement, fly ash cement, masonry cement, high phosphate cement mixed An example is cement. Typical examples of the divalent or higher metal salt of higher fatty acid include zinc salts of stearic acid and palmitic acid, aluminum salts, calcium salts, barium salts, magnesium salts, nickel salts and the like. A divalent or higher salt of a water-soluble polymer containing a carboxyl group means that the water-soluble polymer is composed of alginic acid, polyacrylic acid, polymethacrylic acid, a cellulose derivative, an alkyd resin, an aminoalkyd resin, or the like. The metals are Zn, Cu, Ca, Mg, Be, SrBa, Al, Ti, Zr,
It is a metal selected from Sn, Cr, Mo, W, Sb, Mn, Fe, Co, Ni and V, and forms a salt with the water-soluble polymer and the metal. Silica dust is a by-product when manufacturing silicon or a silicon alloy by an electrothermometallurgical method. Desirable silica dust means a particle size of about 0.1 to 1.0 μ, a specific surface area of about 5 to 50 m ² / g, a bulk specific gravity of about 0.1 to 0.3, and a SiO ₂ content of 60% by weight, preferably 80% by weight or more. It is a thing. Acidic metal oxides are ZnO, Cr ₂ O ₃ , MnO, Mn
O ₂ , FeO, CoO, PbO and the like, and as the phosphate, aluminum phosphate, calcium phosphate, zinc phosphate, thallium phosphate, strontium phosphate, barium phosphate,
Magnesium phosphate, manganese phosphate, etc., borate such as zinc borate, magnesium borate, manganese borate, lead borate, nickel borate, calcium borate, etc., and sulfuric acid as divalent metal sulfate. Magnesium, zinc sulfate, calcium sulfate, and barium sulfate can be exemplified, and examples of the divalent metal sulfite include calcium sulfite, magnesium sulfite, zinc sulfite, and copper sulfite. In the present invention, while the adhesion of the film formed from the conventional composition in which the first component is blended with the first component was insufficient, this was solved by blending the first component to the first component. It is a thing. The details of such effects are unknown, but the present inventors have found that the carbonate or complex carbonate that is sparingly soluble or insoluble in water, which is the third component among the above three components, and that can decompose at about 700 ° C. or lower. Carbonate ions present in trace amounts in the alkali of salts or their minerals react with the water-soluble alkali silicate which is the first component, and assist the curing reaction of the curing agent of the water-soluble alkali silicate of the first component. I'm guessing. Also, it was difficult to form a thick film only by mixing the first component and the first component, but by adding the first component to this, a considerably thick film can be obtained, and the film thickness should be several tens mm. It seems that it has become possible. Furthermore, although the film formed essentially of the first component and the first component is nonflammable and contributes considerably to fire protection, the degree thereof is extremely low. On the other hand, according to the composition of the present invention, it became clear that the degree of film thickness and the decomposed gas of the first component markedly enhance the fire resistance. Furthermore, the composition of the present invention can be applied to various types of equipment, and is probably due to the fact that it can be made into a thick film, but it can be applied not only to cement substrates but also to wood materials and metal materials. It adheres fairly well and helps prevent corrosion of the substrate.

Next, in the present invention, in the above thickening, the weight of the coating itself becomes large, and a foaming technique can be adopted for the purpose of reducing the weight so that the coating does not come off. The metal-based foaming agent of the first component is used as a compounding substance.

In the present invention, various metal elements and metal alloys or intermetallic compounds can be used as the metal-based foaming agent as the first component. As the metal element, the periodic table IB, II A, II B, III
A, III B, IV A, IV B, VA, VB, VI B, VII B, VIII
Those belonging to the group are preferable, and examples of such metal elements include Cr, Mn, Ti, Zr, V, Si, Ge, Sb, Co, Ni, Cu and Z.
n, Al, Ca, Sn and the like, particularly Ti, Zr, V, Al, S
i, Ge, Sb, Zn and the like are preferable. Incidentally, in the present invention, semi-metal elements such as B and As can also be used. Typical examples of alloys and intermetallic compounds (chemical bonds between metals or between metals and nonmetals) include Al-
Si, Al-Ti, Al-Mn, Al-Cu-Si, Al-Cu, Zn-S, Zn
-Sn, Cu-Si, Fe-Si, Si-Ni, Co-Sb, etc. are mentioned. The above-mentioned first component is usually used in the form of fine powder of one kind or two kinds or more, and it is particularly preferable to use it in the form of fine particles of 150 μm or less.

Furthermore, in order to improve the efficacy of the first component, a foaming stabilizer of the first component is added.

The foaming stabilizer as the first component in the present invention is silica gel, zeolite, carbon black, activated carbon, talc,
Inorganic substances selected from Mike, Palygorskite, and Sepiolite, surfactants (excluding metallic soap), and organic substances such as animal proteins and dimethylsilicon derivatives conventionally known as cement-based foaming agents can be used. A wide variety of surfactants can be used in this case, for example, as an anionic one, sodium polyoxyethylene alkyl sulfonate, sodium alkylnaphthalene sulfonate, etc., and as a cationic one, lauryl trimethyl ammonium hydride. Examples of the quaternary ammonium salt include polyoxyethylene glycol laurate as a nonionic one, and as an amphoteric one, n-alkyl-β-aminopropionic acid sodium soda, polyoxyethylene alkyl ether phosphate and the like. it can.

The first component mainly has a function of making the dispersed state of the first component uniform in the composition and stabilizing the foaming state, and is effective for generation of fine bubbles.

When the foaming stabilizer is an inorganic substance, it is usually preferably used in the form of powder having a particle size of 200 μm or less.

The mixing ratio of the above-mentioned first component to the first component is difficult to be constant depending on the type of each component used, desired bulk specific gravity, strength, conditions during curing reaction, etc., but is usually as follows. That is, Based on the solid content of the first component, with respect to 100 parts by weight thereof, the first component is 20 to 500 parts by weight, preferably 50 to 300 parts by weight, and the first component is at least 1 selected from hydraulic cement and silica dust. In the case of seeds, it is 15 to 350 parts by weight, which is a divalent or higher metal salt of a higher fatty acid, a divalent or higher metal salt of a water-soluble polymer having a carboxyl group, an acidic metal oxide, a phosphate or a borate. And at least one selected from divalent metal sulfates and divalent metal sulfites, the amount is 3 to 30 parts by weight. The second component is 2 to 50 parts by weight, preferably 5 to 40 parts by weight. The first component is 5-250 parts by weight when it is an inorganic powder, and 0.5-part by weight when it is an organic substance.
18 parts by weight. Generally, if the first component is present in excess, the adhesion is good at the initial stage, but since the water resistance is poor, it immediately decreases, and even when obtaining a lightweight body, the bubbles are not stable and the foaming state tends to become uneven. . When the amount of the second component is small, the fluidity of the composition itself tends to decrease, causing fluffing during the construction, delaying the curing reaction, and poor water resistance.
In particular, if the amount is less than 20 parts by weight, one of the performances intended by the present invention can be obtained.
It is not possible to obtain the waterproof performance. On the other hand, when the amount is more than 500 parts by weight, the relative ratio of the binder decreases, the adhesion is extremely deteriorated, and uniform and fine bubbles are hard to be generated when obtaining a lightweight body. The second component plays an important role in the curing reaction of the composition, and when it is more than 350 parts by weight in the case of (I) and more than 30 parts by weight in the case of (II), the curing is too quick and sufficient adhesion cannot be obtained. Moreover, when the film is thick, cracking is likely to occur. Conversely, when the amount is less than 15 parts by weight in the case of (I) and less than 3 parts by weight in the case of (II), it takes time to cure and the water resistance is lowered. Tend to do. The first component will foam stably only when used in combination with the first component, but if it exceeds 50 parts by weight, it will foam too much and the cured film will weaken, and if it is less than 2 parts by weight,
The purpose of weight reduction cannot be fulfilled. Similarly, the third component is (III)
When it is less than 5 parts by weight, when it is more than 250 parts by weight, when it is less than 0.5 parts by weight in case of (IV), and when it is more than 18 parts by weight, the foaming stabilizing effect cannot be exerted and the strength is lowered. cause.

In the present invention, the above-mentioned first to second components are mixed in the form of a paste in the presence of water, which is the first component, and no special method is used at this time. However, a satisfactory film cannot be formed unless it goes through a paste-like form.
The water as the first component can be blended by using the water-soluble alkali silicate as the first component as an aqueous solution.

In the present invention, in order to further improve the fire protection performance of the composition for forming an inorganic film, as one filler component, for example, a substance having a high degree of hydration, that is, allophane, boehmite, borax, etc. in a broad sense. The combined effect can be observed with hydroxides such as aluminum hydroxide. In addition, various fillers may be added as needed, as long as the stability of the composition for forming an inorganic film of the present invention is not impaired.

The embodiments will be described below. However, the performance test in the examples was conducted by the following method.

(1) Curing end time: The time when the weight of 500 g placed on the cured body does not sink. (Unit: minutes) (2) Adhesion: Adhesion test method specified in JIS A 6909 (3) Water-resistant adhesion: After the cured product is immersed in water for 96 hours,
According to the adhesion test of (2) above.

(4) Bulk specific gravity: According to JIS A 1161.

(5) Compressive strength: According to JIS A 1161.

(6) Bending strength: According to JIS Z 2248.

(7) Adhesion after heating: After heating in an electric furnace at 500 ° C. for 24 hours, the adhesion test of (2) above is performed.

(8) Compressive strength after heating: After heating in an electric furnace at 500 ° C for 72 hours,
According to the compressive strength test of (5) above.

(9) Fireproof performance test: 300 × 300 × 5 mm steel plate was applied to a thickness of 5 mm in a furnace preheated to 800 ° C, a dry test plate was pressed against it, and the temperature of the back surface steel plate was measured. temperature
Fireproof performance was defined as the elapsed time until the temperature reached 260 ° C.

The components used in the following examples are as follows.

Example 1 As the first component, 4 kg of No. A-1 sodium silicate aqueous solution
Collect (1 kg of solid content) in a polyethylene container (content 18 liters). On the other hand, 4 kg of No. B-1 hydrozincite powder as the first component, 0.2 kg of No. C-2 zinc oxide as the first component, and 200 mg of No. D-1 metallic silicon powder as the first component.
g, 1 kg of No. E-1 silica gel as the first component is collected to prepare a mixed powder. Next, the mixed powder is added to the aqueous solution of the first component and mixed and stirred at room temperature to form a uniform paste. When this paste was quickly applied to the surface of a hard asbestos slate to a thickness of about 2 mm, the plastering of the plastering iron was good, and the work was easy and the smoothness was good. About 30
After a minute, the foaming reaction was started, and after 3 hours, foaming and curing were completed. When the above-mentioned test was conducted on this lightweight body, the following results were obtained.

(1) Curing end time (hours) 3 (2) Adhesion (kgf / cm ² ) 2.5 (3) Water-resistant adhesion (kgf / cm ² ) 2.5 (4) Bulk specific gravity 0.5 (5) Compressive strength (kgf / cm ² ) 70 (6) Bending strength (kgf / cm ² ) 15 (7) Adhesion after heating (kgf / cm ² ) 2.9 (8) Compressive strength after heating (kgf / cm ² ) 110 (9) Fire performance test ( Min) 15 Example 2 4 kg of No.A-1 aqueous solution of sodium silicate
Collect (1 kg of solid content) in a polyethylene container (content 18 liters). On the other hand, No.B-1 hydrozincite powder as the first component 4kg, No.C-1 alumina cement 2kg as the first component, No.D-2 aluminum copper alloy powder 200g as the first component, the first component As a result, 1 kg of No. E-2 activated carbon powder was mixed to obtain a composition for forming an inorganic film, and when this paste was quickly applied to a hard asbestos slate surface to a thickness of about 2 mm, a plastering iron The slip was good, the work was easy, and the smoothness was good. The foaming reaction started after about 40 minutes, and the foaming curing was completed after 5 hours. The test results for this lightweight body are shown in Table 1.

Example 3 4 kg of No. A-2 potassium silicate aqueous solution as the third component
Collect (1.2 kg of solid content) in a polyethylene container (content 18 liters). On the other hand, 4 kg of No. B-2 magnesium carbonate as the first component, 0.2 kg of No. C-2 zinc oxide as the first component, 200 g of No. D-2 aluminum-copper alloy powder as the first component, as the first component. 1 kg of No.E-2 activated carbon powder was blended to obtain a composition for forming an inorganic film, and when this paste was quickly applied to the surface of a hard asbestos slate to a thickness of about 2 mm, the plaster of a plaster for a plasterer The work was good and easy, and the smoothness was good. The foaming reaction started after about 10 minutes, and the foaming curing was completed after 1 hour. The test results for this lightweight body are shown in Table 1.

Comparative Example 1 The results shown in Table 2 were obtained using the same method as in Example 1 except that calcium carbonate was used as the second component in Example 2.

Comparative Example 2 The results shown in Table 2 were obtained using the same method as in Example 1 except that calcium carbonate was used as the third component in Example 3.

(Effect) Comparing the test results of each of the Examples and the test results of the Comparative Examples, the Comparative Examples have inferior adhesive properties and water-resistant adhesive properties to the Examples, and a large difference occurs in the fire prevention performance test. In particular, it was found that the inorganic coating films formed by the respective formulations of the examples had a bulk specific gravity of 0.7 and were excellent in adhesiveness despite being lightweight.

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Claims (1)

(57) [Claims] 1. A carbonate or complex carbonate or a mineral thereof, which is sparingly soluble or insoluble in water and can decompose at about 700 ° C. or less with respect to 100 parts by weight of a water-soluble alkali silicate, 20 to 50.
0 part by weight, the water-soluble alkali silicate curing agent is (I) hydraulic cement, 15 to 350 parts by weight of at least one of silica dust, or (II) a metal salt of a higher fatty acid having a valence of 2 or more, and a carboxyl group. 3 to 30 parts by weight of at least one of a divalent or higher metal salt of a water-soluble polymer, an acidic metal oxide, a phosphate, a borate, a divalent metal sulfate, and a divalent metal sulfite. And 2 to 50 parts by weight of a metal-based foaming agent, and as a foaming stabilizer, (III) at least one kind of zeolite, silica gel, talc, mica, carbon black, palygorskite, sepiolite, and activated carbon 5 to 250 parts by weight or (IV) ) 0.5 to 1 of surfactant (excluding soap), dimethyl silicone derivative, and animal protein-based foaming agent
An inorganic film-forming composition containing 8 parts by weight of water as an active ingredient.