JPH0714801B2 - Method for producing aqueous film-forming inorganic compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field) The present invention is a coating material for paper, fibers, cloths, etc., which prevents ignition and enhances heat resistance. TECHNICAL FIELD The present invention relates to a method for producing an aqueous film-forming inorganic compound having various fields of use which, when impregnated, prevents ignition, flame and smoke generation, becomes a rust preventive paint for metals, and becomes a fire resistant adhesive with ceramics.

(Prior art and its problem to be solved) Sodium silicate has been used as a conventional inorganic adhesive or coating material, but it has a heat-absorbing property and is easily carbonized to produce white fluff, which easily causes shrinkage cracks and peels even when solidified. There are drawbacks such as. There is also a method of improving the water resistance by adding fluoride to the sodium silicate, but it is not sufficient. Silica gel and silica alkoxide are also commercially available, but they have no film-forming property and are modified with an organic compound to form a film-forming compound, but they did not become a high temperature refractory. Further, the fluororesin, which is a compound of Freon and an organic substance, did not become a refractory even though it had more heat resistance than general synthetic resins.

In addition, a metal and ammonia, silicic acid, phosphoric acid or a salt thereof,
There is a proposal to form an aqueous film-forming inorganic compound with an alkali metal (US Patent Nos. 4,117,088 and 4,029,747,
No. 4,117,099 and JP-A No. 51-132196), there is a problem that they do not have film-forming properties.

(Means for Solving the Problems) It is generally explained that the hardening phenomenon starts when the components dissolve and become supersaturated to form a gel bond with the crystal structure.
Even if silica gel, sodium silicate, pozzolan, fly ash, etc. are added to the aqueous inorganic complex compound of the above-mentioned US patent so that, for example, silicon (Si) as a metal component is in a large excess, the film is cured to form a flexible film. It did not give a coating. Further, a water-soluble material such as sodium fluorinated sodium or sodium borosilicate does not form a coating film even when dried, and is merely powdered. Glass is a compound of silicic acid, boric acid, and an alkali metal, but it is not a flexible water-soluble coating material. As mentioned above, although Teflon is a fluoride, it is not a polymer coating only with an inorganic substance. An object of the present invention is to provide a solvent-free aqueous film-forming inorganic compound which is an inorganic compound, has a high molecular weight, and forms a flexible coating film.

That is, in order to form a film like an organic paint, it is necessary to use a polymer, and fire and flame resistance are caused by a heat-resistant film-forming product that blocks the supply of oxygen. A fireproof and flameproof coating suitable for textiles must be a flexible heat resistant coating. On the other hand, if the price is not low, versatility does not occur, so a polymerization method that is solvent-free and has high productivity must be used. The present invention has solved all the above problems.

The aqueous film-forming inorganic compound produced according to the present invention is a mineral acid compound that hydrates a metal to dissociate boric acid or hydrofluoric acid from a mineral acid, or a mineral acid compound (hereinafter collectively referred to as mineral acid compound).
And only by reaction with alkali metals. For example, the reaction product of Si, F, and Na is considered to be sodium silicate,
It has low solubility and does not become an aqueous solution with a solid content of 2.45% or more even at 100 ° C. Also, Si, B and Na are considered to be sodium borohydride and do not become an aqueous solution as described above. However, in the aqueous solution of the present invention, even if the solid content is 45%, the element is Si
Only F, Na, and Si, B, Na are analyzed.

According to said U.S. patent, for example, in the local area where metallic silicon is at the bottom of the reaction vessel and the caustic soda flakes are in drop contact therewith, silicon, caustic soda,
The reaction of sulfuric acid is said to occur. However, when the metal silicon block was excessively stuffed at the bottom of the reaction vessel and the dilute solution of boric acid was present in the half of the vessel, the caustic soda flakes were sprinkled at one time enough to cover the silicon surface, and the caustic soda flake was If it is a local area reaction, the reaction should occur all over the bottom at one time, but not at the same time, the parts are intermittently consumed, and the dissolved components are consumed so that they react according to the solubility in the bottom area. It was observed that the reaction was not a local area reaction. Similarly, 1m / m metal
When observing the reaction with aluminum wire of diameter, it is possible to observe the reaction that white clouds crawl along the aluminum wire as well as around the caustic soda flakes, even if caustic soda flakes are scattered. . Also, wrap the metallic silicon in an iron mesh, pull it up by 5 cm or more from the bottom of the reaction container and hang it in the air, put caustic sozo flakes on the bottom, even if it does not come into direct contact with the silicon, just as when it comes into direct contact Foaming was generated to start the reaction.
As is clear from the above, according to the present invention, if the caustic soda flakes that have settled at the bottom of the reaction vessel reach a certain solubility, the dissolution is stalled and the caustic soda flakes are consumed by the reaction and further dissolved or if the solubility changes due to convection, further dissolution occurs. Shows
It shows that it is different from the local area reaction of flakes referred to in the US patent. The aqueous film-forming inorganic compound produced according to the present invention is produced by an exothermic reaction or heating by hydrated boric acid or hydrofluoric acid participating in a concentrated solution reaction of a metal solid and an alkali metal. Since the dissolution of borax and sodium fluoride is lower than that of acid, it controls the reaction. In the case of controlling the reaction by cooling the boiling reaction in the summer, and in order to control the temperature so that it does not reach the boiling point, a hafnium compound containing hafnium, zircon, or one or more of zirconia by-product silica (hereinafter zircon). (Referred to as "classes") is added to 0.5% to 100% of the mineral acid compound to control the heat generation and react. 50 in winter
The reaction is accelerated by heating above ℃.

The mineral acids include hydrogen fluoride, which hydrates to dissociate hydrofluoric acid, hydrofluoric acid, sodium fluoride, ammonium fluoride, and boric acid, which hydrates and dissociates boric acid, borax, sodium borohydride, or boron. Hydrofluoric acid and its ammonium metal salt.

If the above diluted mineral acid is used in the reaction solution, the solubility of the alkali metal is increased and a strong alkaline product (PH 11.5-12.6) can be prepared. Also, if a concentrated solution acid is used, the solubility of alkali metals is low and weakly alkaline (PH7-9) products can be produced. If the reaction solution has a specific gravity of 1.1 or more, the solid content is 10%.
The above-mentioned aqueous solution having a pH of 13 or less is a film-forming inorganic compound produced by the present invention, which is different from sodium fluorosilicate or sodium borohydride. At the bottom of the reaction vessel, while reacting a concentrated solution of metal and alkali metal flakes, allow a gaseous mineral acid or concentrated aqueous solution mineral acid to participate in the reaction, or to add a mixture of concentrated mineral acid and metal to alkali metal flakes or 10 times The following concentrated solution was fed into the bottom of the reaction vessel and reacted to obtain a reaction product solution having a specific gravity of 1.2 or more and PH9 or less. In any case, heating is required when self-heating above 50 ° C is not generated, and it is necessary to add or cool the zircon so that it does not boil when it is expected to reach 90 ° C to 100 ° C. is there. Since the solid alkali metal has a low solubility in a concentrated mineral acid solution, it needs to be heated or gradually reacted. In this invention, even if each component is excessively blended, each component does not dissolve beyond the dissolution product, and the reaction supernatant is almost constant.

The film-forming inorganic compound was applied to an iron plate and dried at room temperature to obtain a 7-micron coating film. The coating does not crack when heated.

In order to strengthen the coating film and accelerate the curing, it is sufficient if the metal component is in a supersaturated state, and if the metal is silicon, silica sol, sodium silicate and pozzolan, or SiO ₂ such as silica fume.
Ingredients, or if the calcined product metal is aluminum, add Al ₂ O ₃ -containing components such as alumina sol, sodium aluminate, or kaolin / bauxide, or the calcined product to the above film-forming inorganic compound to cause a large excess of the metal component. When the film-forming inorganic compound described above is used, the film formation is fast and the surface hardness is high even when the film is cured at room temperature. The amount of the metal-containing component added is, for example, SiO ₂ or Al ₂ O ₃
In terms of workability, around 20% within 30% of the solid content of the present invention is suitable for workability. As a result of this improvement, for example, the pencil hardness is improved from 5H to 9H.

As a general-purpose method, there is a heating concentration method for increasing the specific gravity so that the film-forming inorganic compound becomes a polymer.
Alcohols (C number 1-18 from methyl to stearyl) are added to the above-mentioned film-forming inorganic compound having a specific gravity of 1.2 in an amount not more than about the same as the solid content. Only the components settle, and the low specific gravity component (low molecular weight) forms the upper layer together with the alcohols. Therefore, by removing the sediment from the bottom of the tank (reactor), the high specific gravity component is about 1.4.
Is obtained. In this case, after mixing alcohols,
Since it takes time for the high specific gravity component to settle,
When diluted mineral acid having a pH of 2 or more (2 to 10 times) is added to the alcohol in an amount of 5% to 30%, the film-forming inorganic compound having a specific gravity of 1.2 produced according to the present invention is mixed with about 20% by volume. It is possible to accelerate the sedimentation of high specific gravity components. Also
Although 99% methanol gels rapidly even at 1%, it is not necessary to add alcohol above the solid content. When alcohols are mixed, the boiling point due to azeotropy is lowered during heating and excess water is released to cure.

When the film is heated to accelerate film formation, surface film formation is accelerated, and excess water is built in, causing blistering. There is a similar tendency even when heated after room temperature curing. Magnesium (Mg), which absorbs water to form hydroxyl groups, and aluminum (A
l), metals such as iron (Fe) and fine powders of its hydroxide of 100 mesh or less are added to the solid content of the film-forming inorganic compound in an amount of 1 to 50% to absorb excess water. Alternatively, due to an exothermic reaction, film-forming blisters at the time of heating and blistering at the time of heating after curing at room temperature can be prevented. Amorphous mineral
Silicic acid with mineral powder calcined above 500 ℃. Alumina hydroxide is also effective.

The film-forming inorganic compound according to the present invention is a noncombustible material and a fireproof material. Furthermore, in order to increase adhesion, tackiness and fire resistance, kaolin, pyrophyllite, clay, clay, amorphous silica (pozzolan / silica fume) mica, vermiculite, and diatomaceous earth are fire resistant at high temperatures. Mullite with. Admixed with alumina forming material, it has adhesiveness and fire resistance of 1000 ℃
Because of the above, it becomes a fireproof and fireproof strong coating film, such as iron, stainless steel, aluminum, ceramic felt, board, etc.
Flexible fireproof adhesive. Viscosity is 100 without addition
~ 200 centipoise thickens to 800-1500 centipoise with the formulation and mixes mineral fibers to further increase transverse rupture strength. However, if the amount of the film-forming inorganic compound is the same or more, the impact resistance is weakened. The adhesive had a tensile peel strength of 30 kg / cm ^{2 from} iron.

The film-forming inorganic compound is hardened by a hydrate that elutes active Ca ions. By mixing quick-lime or light-burnt dolomite, or a hydration exothermic material that is a content thereof,
It cures quickly by removing excess water and ion exchange. It is also hardened by general cements that dissolve calcium hydroxide. It is also effective for cement that quickly hardens due to heat generation, such as waterproof cement. Further, the magnesia cement causes a curing reaction with the film-forming inorganic compound even without a curing agent. Similarly, a mixture hydrated with metallic aluminum, magnesium, iron, or an oxide thereof, and generating heat, also works effectively. The amount of addition is the same as the excess water of the film-forming inorganic compound up to 3 times.

The film-forming inorganic compound according to the present invention is considered to be a complex compound polymer. Therefore, there is a drawback that the boundary between the hydroxyl group and the excess water is not clear, and the surface film formation is faster than heating or normal dry dehydration. As a means for solving this, the hydroxyl group absorbs water as described above. A method of mixing a metal oxide, a hydroxide or a fired product of an amorphous metal is effective. In addition, the inlet temperature is 150 ℃ ~ 600
The film-forming inorganic compound can be sprayed on a dryer at ℃ to produce dehydrated beads of 5 to 80 microns. With a Kett moisture meter, it was possible to dehydrate to 2 to 7%. When this was freely mixed with the film-forming inorganic compound in an amount of 1 to 100% and applied, a coating film with good build-up could be obtained. Glass, carbon,
Fibers such as cotton, synthetic fibers, and wool are made up of hundreds of yarns and contain air bubbles. A synthetic resin having an alcohol group is preferable as the coating agent that substitutes for the bubbles and reacts with the film-forming inorganic compound. For example, polyvinyl alcohol is suitable as an undercoat because it has alkali resistance, and even if soluble in water, it condenses with the film-forming inorganic compound and becomes insoluble.

Next, the raw materials of this invention will be described. As the metal, one or more of the metals belonging to Groups I to VIII of the Periodic Table can be used, but in general, metal silicon and metal aluminum are preferable, and the reactivity is high if the surface area is large, medium, small lumps, Any of grains, foils or wires may be used. As described above, when it is placed in a mesh and slightly lifted from the bottom and suspended in the air, it can be used for several reactions without surface coating with reactants. Of the mineral acids or sub-mineral acids, any mineral acid compound that dissociates to generate boric acid or hydrofluoric acid may be used, and borax and sodium fluoride may also be used. As described above, a gas body can also be used. Although the reaction solution boils due to excessive heat of reaction in the summer, when the zircon is introduced (the powder, lump, etc. may be used), the reaction is violently exothermic but it does not result in boiling, which is safe. Zircon by-product silica fume contains a small amount of hafnium, but may be added in the same amount as silicon. The alkali metal may be any of sodium (Na), potassium (K), and lithium (Li). grain. flake. A solid form such as 10 times liquid or less-generally 5 times liquid or less-can be used. The component that makes the metal component excessive is silica. Alumina sol and alkali metal salts such as sodium silicate and sodium aluminate,
The above-mentioned amorphous minerals and the above-mentioned oxides and hydroxides which become the hydroxides of the fired products thereof may be used alone or in combination. As an added alcohol for obtaining a high specific gravity product, methyl alcohol rapidly gels, ethyl alcohol is good but expensive, so denatured alcohol is good, and isopropyl alcohol (IPA) gives good yield and economic efficiency. Is high. Suitable alcohols also differ depending on the type of mineral acid. If it acts as a precipitate, it cannot be said to be outside the scope of the present invention because it is a carbonic acid number or a modified product. If a 20% solution of alcohol is added with 20% of PH2 solution of hydrochloric acid as a mineral acid, the sedimentation rate will be faster. The acid may be any of mineral acids, but other mineral acids are preferable because the raw material mineral acid of the film-forming inorganic compound and the same mineral acid are compatible with each other.

Fillers that obtain fire resistance and film thickness are storage stable kaolin, amorphous silica-containing mineral powder, silica fume,
Magnesium hydroxide, aluminum hydroxide, or those which hydrate to dissolve them, and fine powder of 100 mesh or less is desirable.

This invention is a reaction with a solid having a higher specific gravity than water or a high specific gravity liquid at the bottom of the reaction vessel, and therefore, in accordance with the theory of dissolution product, each component does not dissolve above a certain amount and does not dissolve even if blended in excess. It remains as a component and the reaction component becomes a supernatant due to convection due to the exothermic reaction, and even if the metal and mineral acid components are in excess, it becomes a product due to the dissolved amount of the alkali component, so it does not have a component ratio like the diluted solution reaction equivalent .

(Effects of the Invention) The aqueous film-forming inorganic compound according to the present invention has two elements of Si, F, Na or Si, B, Na according to the analysis results (Table 1) of the Kanagawa Prefectural Industrial Laboratory. Being a group composition,
It was confirmed that the solid content was 20% or more, and it was found that it was not low-solubility sodium fluorinated sodium or sodium borohydride. In each of the above cases, a film was formed on the iron plate, and cracks and peeling from the iron plate did not occur at any thickness of 5 μm to 100 μm.

The substances contained in each sample in Table 1 are values excluding water. Therefore, the total number is less than 100%, but the balance is water.

The structure of the film-forming inorganic compound according to the present invention is [Aa Bb] _R Cc Dd or [Aa Bb Cc Dd] sCp Dq, where A ... Si, Al B ... FH, H, BH ₃ , B ₂ O ₃ C ... Na, K, Li D ... H ₂ O, OH moles ... a, b, c, d, p, q, R, S are estimated.

The product according to the present invention is coated on a 30-micron iron foil.
When it was dried at 100 ℃, it was formed into a film of 6 microns and the radius of curvature was 2m /
Although it was bent at 90 degrees at m, no peeling crack occurred. The heat-dried product had a pencil hardness of 3 to 5H. The iron foil, 50 ℃
× 90% RH × 7 days, no rust was generated, and rust preventive power was generated.
When the product according to the present invention was applied to a polyester non-woven fabric, the elemental Si-B-Na product became softer than the Si-F-Na product, but all of them were flexible and did not crack or peel, and were immediately ignited by a lighter. There was no. It was applied to a 50-micron iron foil and dried at 80 ° C. The thickness was 7 microns and the hardness was 9H or more. The uncoated product was cut by 50 times of bending, but the coated product according to the present invention could not be cut up to 120 times.
A 3.2 m / m-thick iron plate was heated with a burner and penetrated in 1 minute 40 seconds. When both sides of this iron plate were heated with a burner after applying Si-F-Na-based invention product, In 4 minutes
It took 10 seconds.

The product according to the present invention has a specific gravity of 1.25 and a solid content of 27
% Si-F-K-based products, isopropyl alcohol (IP
A) 20% (volume) was added and mixed and left to stand. One hour later, the sediment was taken out and the specific gravity was 55% (by weight) 1.
Got 45 products. (This is referred to as P-Si-FK). Similarly, the specific gravity of Si-B-Na-based products is 1.23, and the solid content is 25%.
Then, 20 parts by volume of denatured alcohol was added and mixed, and after 1 hour, a product having a specific gravity of 1.43 with a yield of 50 parts by weight was obtained (this was P-Si-B
-Na). On a steel bar with a diameter of 20 m / m, the P-Si-F-
K was applied to a thickness of 10 microns and melted with an oxygen burner,
It did not burn like paint, and the fusing part did not rise. Around the melting point of about 200 ° C., the P-Si-FK was coated and left outdoors for 6 months, but no rust was observed.

According to the DTG analysis result of the product according to the present invention,
Large dehydration at 180 ℃, that is, excess water dehydration, then 600 ℃
At around 800 ° C, a small peak of water desorption was observed, and the change in weight was slight. However, when these are coated on an iron plate and heated to 200 ° C. for dehydration of excess water, surface film formation is rapid, dehydration of excess water is delayed, and blisters often occur. It is effective to use a metal compound or a mineral calcined powder that hydrates to form a hydroxide or crystal water and absorbs excess water, for example, a Mg or Al compound or a diatomaceous calcined powder. The viscous P-Si-F-
When K or P-Si-B-Na was added in an amount of 10 parts by weight or less and about 5 parts by weight, a remarkable effect was exhibited. 180 iron plate coated to a thickness of 10 microns
No blister occurred when dried at ℃ or heated at 1000 ℃ with a burner.

Since the product according to the invention is an aqueous solution, the coating thickness is around 10 microns. In order to increase the coating thickness to enhance fire resistance, a filler must be mixed, but storage stable kaolin, amorphous silica fume, etc., pyrophyllite sinter etc. are good, and pyrophyllite Fire resistance occurs due to dehydration of water of crystallization, mullite phase, and cristobalite phase change. Tackiness can be imparted by diatomaceous earth, and transverse rupture strength can be imparted by mineral fibers. The above mixture is a metal,
For example, when it is used as a laminated sheet using an adhesive material of stainless steel foil and alumina silica paper, it is flexible and
There was no peeling even when heated to 00 ° C and there was fire resistance.

On the other hand, a transparent and thick coating requires a transparent filler such as quartz, magnesium hydroxide or aluminum. When this invention product is spray dried at a temperature of 200 ° C or higher, most of the excess water is dehydrated and
Was left, and fine ceramic beads that remained reactive were obtained. When viewed under a microscope, it was a spherical transparent product of 5 to 80 microns.

Since the product according to the present invention is an inorganic substance, it does not burn even if it is exposed to high heat.
The temperature may be set to 600 ° C. Therefore, it was possible to increase the amount of spray supply and obtain a large amount of yield. As a result, low cost fine ceramic beads were obtained.

The product according to the invention contains 3 to 20% magnesia cement.
In addition, it becomes the curing agent. Therefore, when the product according to the invention is mixed with magnesia cement as a filler, it cures. Cement, lime-based hydration exothermic material, quicklime, and dolomite, which generate heat at room temperature or when hydrated and elute calcium component, are mixed as fillers and act as a hardening agent as described above. It adhered to metal, had little curing shrinkage, and had fire resistance of 1000 ° C.

As described above, when the product according to the present invention is formed into a film by heating, it is heated under reduced pressure to dehydrate excess water, for example,
Since 740 mm Hg 60 ° C is equivalent to atmospheric pressure 180 ° C-200 ° C,
Although effective, continuous production is difficult. Further, since the fiber or felt-like product is composed of a large number of yarns and contains air therein, if the product according to the present invention is hermetically sealed and heated, the film formation according to the present invention is destroyed due to expansion. , Neither fire resistance nor flexibility. In these cases, there is alkali resistance, PVA having an alcoholic acid group, acrylic, or polysaccharide protein as the undercoat material, and also used for air displacement, when the product according to the present invention as the overcoat material, condensation reaction It chemically bonded, dried at low temperature without blistering, retained flexibility, and gave fire protection.

(Example-1) At the bottom of a plastic container with a capacity of 1
/ m ~ 10m / m grain, 300g densely packed, borax 10 hydrate 5 times solution 3
I put in 00cc. In addition, a few pieces of flaky caustic soda,
It fell on the silicon but diffused, causing no reaction on the silicon surface. Next, triple solution of caustic soda 50
When cc was added, it settled due to the difference in specific gravity and generated bubbles from the metal surface and reacted. The solution sucked up from the bottom with a dropper had a thick PH14, but the surface liquid was only PH9.5. However, the temperature was 21 ℃ and the water temperature was 18.4 ℃.

(Example-2) A 0.5 m / m diameter metallic aluminum wire having a purity of 99.9% was cut into a length of 10 cm in the container of Example-1 described above, and 200 g was tightly placed at the bottom. After adding 300 cc of a 10-fold solution of boric acid, one scoop of flaky caustic soda was dropped. The reaction did not occur only around the fall of the caustic soda, but the reaction spread as white clouds crawl along the aluminum wire. That is, depending on the solubility of the bottom of the reaction vessel, an alkaline solution was generated to start the reaction. It was acknowledged that this was not the local area reaction of solid alkali as shown in the previously mentioned US patent.

(Example-3) Metallic silicon was squeezed at the bottom of the reaction vessel in the same manner as in Example-1, 300 g of 200 g of water was added to 100 g of sodium fluoride, and 50 cc of PH13 caustic potash was added to it. In order, put the caustic potash solution in a container, then add metallic silicon, and gradually add 300 g of the sodium fluoride solution,
Since it was the above-mentioned salts, the reaction did not start immediately, but the reaction gradually occurred. However, the temperature was 18 ℃ and the water temperature was 16 ℃.

(Example-4) Under conditions of an air temperature of 21 ° C and a water temperature of 18 ° C, 15 kg of flaky caustic soda was put into a 250 stainless steel drum, and then,
50 water was poured. Immediately, it was observed that flakes partially diffused to the bottom to form a concentrated solution. However, all remained undissolved and remained at the white, solid, bottom. Next, when 25 kg of a metal silicon block having a diameter of 5 to 10 cm was charged, bubbles were continuously generated from the silicon surface due to the reaction with the concentrated caustic solution at the bottom. Next, 25 kg of borax 10 hydrate was mixed with 20 water, and 45 kg thereof was put into the stainless steel drum, and water was further added until the water became 100. The temperature of the drum wall reached 90 ° C and boiled, so 50 more water was added and left to stand. The next day, the supernatant PH12.6, specific gravity 1.23, solids 24
% Transparent solution was transferred to another stainless drum to obtain 100.

Since metallic silicon and unreacted caustic soda remained undissolved at the bottom, 15 kg of borax was added, water was poured until the total amount reached 150, and then raw steam was blown in to raise the temperature to 50 ° C, and the reaction was restarted. . The next day, 100 was obtained, which was a clear liquid with a pH of 12.2, a specific gravity of 1.203 and a solid content of 21%. That is, even if the reaction components were excessive, the same reaction product was obtained by transferring the supernatant liquid having a specific gravity of 1.1 or more and PH of 12.6 or less.

(Example-5) Under conditions of an air temperature of 25 ° C and a water temperature of 21 ° C, a diameter of metallic silicon is 30 m /
22 kg of m or less, 10 kg of boric acid, and 3 kg of caustic potash were mixed in solid form, put into the stainless steel drum of the previous example, and water 70 was further poured. Immediately, an exothermic reaction at 50 ° C or higher was started, and the next day, a crystalline solid matter was broken out. When 1 kg of caustic potash was added to this, a transparent viscous solution was obtained, which was filtered with cotton cloth. PH1
2.2 Clear liquid 12.5 (about 18 kg) with a specific gravity of 1.44 was obtained. The residue was left to stand and a supernatant was obtained. It was a transparent liquid with a pH of 12.2 and a specific gravity of 1.45. The residue contained 5.5 kg of fine-grained metallic silicon.

(Example-6) The amount of the borate sand compound of Example-4 was changed to 10 kg, 15 kg, 20 kg, 30 k.
The reaction was stopped when pH of the reaction solution was 12.6 or less and the specific gravity was 1.2 or more, instead of g, 40 kg, and 50 kg. In all cases, a transparent liquid having a pH of 12 to 12.6, a specific gravity of 1.2 or more and a solid content of 20% or more was obtained. The reaction results according to the theory of dissolution product at the bottom of the reaction vessel are shown, and the reactants are the same.

The above Examples-4 to 6 were analyzed by a Shimadzu spectroscope, but there were no elements other than Si, B, Na and K.

(Example-7) The borax of Examples-4 to 6 was replaced with sodium fluoride, and when the supernatant became PH12 to 12.6 or less and the specific gravity of 1.2 or more, it was transferred to another stainless steel drum. ~ 12.6, specific gravity 1.2
A transparent liquid having a content of ˜1.35 and a solid content of 20 to 35% was obtained.

An example thereof, the stainless steel drum used in the above example, the metal silicon lump of diameter 20m / m ~ 100m / m 40kg, and then sprinkled with flake caustic soda 15kg, water temperature 15
When 50 ° C. water was added, an alkaline concentrated solution was immediately formed, a surface reaction with metallic silicon was caused, and bubbles were continuously generated. Next, mix 40 kg of sodium fluoride with 50 parts of water,
Was charged into the above reaction tank. Since it reacted vigorously and started to boil, water 60 was added to cool it. After that, the liquid temperature became 40 ° C or lower, so when the raw steam was sucked in and heated to 50 ° C or higher, the reaction became active again. The supernatant is PH12.6, specific gravity 1.
Since it became 24, the transparent supernatant was transferred to another stainless steel drum and allowed to stand. At room temperature, it had a pH of 12.4 and a specific gravity of 1.25. Even if 100 cc was taken and 20 cc of 20% hydrofluoric acid solution was gradually added, they did not become compatible and did not gel. For comparison, the above hydrofluoric acid was added to a 35% sodium silicate solution to cause gelation. The product according to the present invention was a clear liquid even if the elements were Si, F and Na.

(Example-8) In Example-2, when 10 g of zircon was added to 300 g of metallic aluminum and 100 cc of a 5 times solution of caustic lithium was added, the solid metal and the concentrated alkali solution caused an exothermic reaction, which was heated to 80 ° C. 35% borax was gradually blown into the bottom of the container through a 3 m / m stainless pipe. Since it became a viscous liquid when it was kept at PH 9.5, the supernatant was put in another container and left to seal. One day later, a semitransparent viscous liquid having a pH of 7.8 and a specific gravity of 1.6 was obtained.

(Example-9) A reaction vessel (5) made of a pressure-tightly sealed stainless steel drum.
In addition, 1 kg of metal silicon with a diameter of around 10 m / m and flake caustic potash
Even if 150g was mixed, the exhaust was piped into the water tank and set so that it would not be discharged into the atmosphere. Pour 2 water from the water injection hole and heat up to 80 ° C, so slowly inject gaseous hydrofluoric acid to the bottom so that the reaction liquid temperature does not fall below 50 ° C.
After occasionally warming and continuing until pH was within 9.5, the reaction was stopped and the supernatant was taken out and allowed to stand. A transparent product with a specific gravity of 1.3 and a pH of 7.6 was obtained. A transparent product having the same viscosity was obtained by using boric hydrofluoric acid instead of anhydrous hydrofluoric acid or caustic soda or caustic lithium instead of caustic potash. In order, PH10 was obtained by spraying solid alkali metal while heating to silicon and 38% hydrofluoric acid, and PH8 and specific gravity of 1.35 were also obtained. According to Shimadzu spectroscopic analysis, Si, F, Na, K,
Other than Li was not analyzed, it was hardened by adding fluoride to sodium silicate, but it was found that the product according to the present invention is a solution even if there is fluoride, and is not a known substance.

(Example-10) The products of Examples-4 to 6 were mixed with 0%, 3%, 10%, 30%, and 40% of sodium silicate as a metal component, and the mixture was coated on a stainless steel foil, and the temperature was 100 ° C. It was cured by heating at 5m / m and tried to bend at 90 degrees. The coating thickness is 20 microns or less and sodium silicate 40
%, No cracks occurred. The hardness was 5H-9H.

Similarly, catalytic conversion of cataloid SA (SiO ₂ 30%) from 1% to
After adding 35% and applying a coating thickness of 10 μm or less onto a stainless steel foil and heating and drying, it was bent at 2 m / m. There was no peeling in either case.

(Example-11) PH7 to 10 produced by replacing the mineral acid of Example-8 with hydrofluoric acid and sodium fluoride, and each product having a specific gravity of 1.1 to 1.6 of PH11 to 12.6,
Alumina sol is converted to solid content based on solid content 0-100
%, And 0 to 50% of sodium aluminate, applied to a 50 micron iron foil to a thickness of 12 microns, dried at 80 ° C., 2 m / m
A bending test was conducted, but no peeling or cracking occurred. The hardness was 3H-9H.

(Example-12) 40 parts of water was added to the products of the specific gravity of 1.25 and PH12.2 of the above-mentioned Examples-6 and 7.
Part, 20 parts of IPA, 20 parts of a mixed water of 20 parts of hydrochloric acid of PH2 were added and allowed to stand. The specific gravity of the sediment containing the supernatant was 1.43 and the yield was 55.
%Met. When 96% methanol 10% is added, the specific gravity is 1.46.
The yield was 45%. The yield with a specific gravity of 1.42 after adding ethanol was 57%. Even with denatured ethanol, the yield was similar.

(Example-13) The viscosity of 100 parts of P-Si-F-Na of the previous example was 420 CPS. When 20 parts of kaolin, 40 parts of pozzolan and 2.5 parts of diatomaceous earth were mixed with this, the viscosity became 1200 CPS. Iron plate (10m / m)
Alumina-silica blanket (12.5 m / m) was pressure-bonded and heated to 1200 ° C., but no peeling or cracking occurred even after 2 hours. Furthermore, when a filler was added to the above to make it 100 parts or more, the viscosity became 2000 CPS.

(Example-14) Excess water excluding the solid content of the aqueous film-forming inorganic compound was used as cement mixing water, and was mixed so that mixing water / cement = 0.35-1. Table 2 shows the results of applying this to a calcium silicate plate at a thickness of 0.5 m / m.

Example 15 In Table 2 of the above example, the inlet temperature was changed from 200 ° C. to 600 ° C. with a spray dryer of Okawara Koki Co., Ltd., and the particle size was observed. The product had a yield of 95% or more based on the solid content, and the water content was reduced to 2 to 5% in the above-mentioned example.

(Example-16) When 20 g of PVA 10% liquid and 20 g of Example-14 were mixed, a gel body was separated, and this was dried to show rubber-like elasticity,
Ignition with a lighter did not cause a flash.

(Example-17) A product obtained by impregnating and drying (70 ° C) 100g / m ² of Nitto Boseki glass cloth in 5% PVA liquid, and then impregnating the product of Example-14, squeezing and post-drying (120 ° C). Was flexible and heated with a 1000 ° C burner, but did not penetrate through the melt.

(Example-18) 10 parts of PVA was mixed with 10 parts of kaolin to undercoat a silica plate. Example 14 was overcoated and dried at 100 ° C., but it did not cause blistering, and it was only 0.1 g / cm ² in a water permeation resistance test using a cylinder.

(Example-19) Add ethylene glycol to cedar, Japanese cypress, spruce, lauan, etc.
A plate of 10 cm × 20 cm × 0.1 cm was impregnated, lifted after 6 hours, the surface gel adhering thereto was washed and dried, then impregnated again in Example-14 and lifted and dried after 12 hours. 850
When heated with a burner at ℃, carbonization occurred but flashover did not occur.

(Example-20) Fig. 1 is a DTG of Example-14. 170 ° C and 470 ° C and 5
There is an endothermic peak and dehydration at 70 ℃ and 670 ℃, but the weight change after 300 ℃ is very small. Figure 2 is a schematic diagram of DTG.

Table 3 shows the results of Example-14 ,.

[Brief description of drawings]

 FIG. 1 is a diagram showing the differential heat and analysis of Table 3. FIG. 2 is a schematic diagram of the weight loss and endothermic pattern in FIG.

Claims (7)

[Claims] 1. A metal aluminum or silicon, a mineral acid compound such as borax, boric acid, sodium fluoride or hydrofluoric acid which hydrates to dissociate boric acid or hydrofluoric acid, and an alkali metal of caustic potash, caustic soda or caustic lithium. When reacting, in water or a solution of the mineral acid compound, to cause a concentrated solution reaction of the metal solid and the alkali metal, further react the mineral acid compound, the reaction heat 50 ℃ or more 100 ℃ A method for producing an aqueous film-forming inorganic compound, which comprises controlling the temperature within the range and forming a film with a specific gravity of the product of 1.1 or more. 2. The method for producing an aqueous film-forming inorganic compound according to claim 1, wherein a metal compound is added to the produced aqueous film-forming inorganic compound to make the metal component excessive. 3. A specific gravity of 1.3, which is produced by mixing an aqueous film-forming inorganic compound with an alcohol with or without a mineral acid.
The method for producing an aqueous film-forming inorganic compound according to claim 1 or 2, wherein the above-mentioned sediment is used. 4. The aqueous film-forming inorganic compound is added with natural or synthetic mineral powder, mineral fibers, or a mineral layered product to increase the viscosity. A method for producing the aqueous film-forming inorganic compound described. 5. The aqueous film-forming inorganic material according to any one of claims 1, 2, 3 and 4, characterized in that a metal compound which becomes a hydroxide or a hydraulic composition is added to the aqueous inorganic compound. Method for producing compound. 6. The aqueous solution according to claim 1, wherein the water-based inorganic compound is used as a top coating material and the synthetic resin-containing material having an alcohol group is used as a base coating material. A method for producing a film-forming inorganic compound. 7. The aqueous solution according to claim 1, which is produced by spray-drying the aqueous film-forming inorganic compound at an input dryer temperature of 150 ° C. to 600 ° C. A method for producing a film-forming inorganic compound.