KR100386666B1 - High concentration boric acid compounds and fire-retardant compositions containing them, or binders and fire-retardants, using them - Google Patents

Abstract

The boric acid compound is mixed with an aqueous solution of a metal ion sequestering agent or an aqueous solution of a wet permeable surfactant so as to have a solubility of at least 5 g / 100 g of water at room temperature, and the mixture is obtained by hydrothermal reaction at 60 ° C or higher. The high concentration boric-acid compound obtained by adding either or both of the silanol salt which has a phosphoric acid or a siloxane skeleton on it.

Fireproof and fireproof material manufactured using the fireproof and fireproof composition containing a high concentration boric acid compound.

Description

High-concentration boric acid compound and fire-retardant composition containing the same or binders and fire-retardant materials using the same

(Background of invention)

(Industrial use field)

TECHNICAL FIELD The present invention relates to a fire protection and fireproof composition containing a high concentration of boric acid compound which can be used for fire protection and fireproofing in a non-pollution manner, while hardening wood and natural fibers.

If there are inorganic binders that make the wood and natural fiber beautiful and durable in the global environment, and at the same time, they become durable, they become durable and become fire and fire resistant materials. This leads to a wide range of applications.

In addition, there is a demand for a fire prevention material that flame-retards daily necessities, clothing, utensils, building materials, and does not generate harmful gas or smoke during a fire. Furthermore, due to the global environment, it is time to save resources by insect-proofing and preserving natural wood, fiber, and paper products.

Since this object can achieve these objectives, this invention can be widely used for various industries. Moreover, it can be used as a pollution-free flame retardant to synthetic resins produced in large quantities.

(Conventional technology)

Conventional natural fibers such as wood, cotton and hemp have been replaced by synthetic resin products, which are petroleum products because of their durability. However, synthetic resin products have a pollution that generates harmful gases and graphite groups during a fire, and commercialized by mixing flame retardant materials to prevent them. These flame retardant fires include halides, phosphorus-containing compounds, nitrogen compounds, metal compounds, and the like, and it has been reported to pay attention to the gases generated during combustion.

In addition, although conventionally used as a boric acid compound flame retardant, they had to be a lean solution. For example, the use of lean solution does not produce fire protection.

In order to make fire resistance and fire resistance, it should not be precipitated and powdered even at the time of normal temperature or a combustion, and since it does not produce an effect unless it is formed into a film, the emulsion was added. However, this is flameproof but not fireproof. In addition, in order to be fire-proof by injecting into wood, the solid must remain to the extent that it dries and covers the surface of a tissue. Phosphoric acid or guanidine sulfate is widely used as a flame retardant, but using a large amount of it as a fire retardant has many problems in terms of its injection and generated gas.

Already, quasi-non-combustible wood in the market is commercialized, but the manufacturing process is not simple and high cost. Urea resins, melamine resins, and phenol resins are used as binders for chip boards, MDFs, and rock wool boards.However, in commercial products, the concentration of synthetic resins is 40 to 65%, but the concentration is actually lowered. It is made of synthetic resin containing concentration before and after. In order to be a fire prevention and refractory binder, it cannot be replaced unless it is the said concentration.

To date, no material has been used to form high concentration coatings with inorganic solutions that are harmless upon combustion. Materials that can be injected or impregnated into wood or natural fibers should be solutions that can be injected into microstructures. In suspensions with particles, no effect occurs.

It is known that boric acid compounds have antibacterial, insect repellent, and mildew prevention effects, and at the same time, they have a flame retardant effect. Conventional preservatives, even if effective for preservation, did not become a preservative. Commercially available flame retardants are put into synthetic resins and put into them to generate and extinguish decomposition gases in the case of fire, and are used in general. However, although they have a short time effect, for example, they maintain a fire protection effect of 10 minutes or more. It was difficult. In addition, many of these decomposition gases contained nitrogen gas and chlor which are undesirable for disaster prevention. The solids concentration of liquid organic or resin products used in commercial raw materials reaches 65%. In terms of solubility, it is 65/35 = 1.857, and the equivalent boric acid compound is about 5% in its known solubility. Therefore, it is necessary to set it as 150-200% of stable solution without precipitation and sedimentation which is considered impossible.

In addition, mixing into a synthetic resin may be carried out in the form of fine powder or coated in a resin surface, and may be put in the form of a coated resin surface. However, in order to obtain a dry body having an action effect, a high concentration product is required.

Inorganic fiber composite products which are made of nonflammable are obtained, but inorganic prepreg products have not been realized. Just like this, we hope for the emergence of flame retardant sheet-like or mole-compounds.

The binder of wood or natural fiber should be neutral and acidic. Inexpensive inorganic flame retardants are boric acid-containing compounds and phosphoric acid compounds, but neither of these forms a film alone. Borax and boric acid have low solubility and do not reach high concentrations. Phosphoric acid can be high but strong.

That is, there was no method of adjusting pH arbitrarily after making it into the high concentration solution of a boric acid containing compound. In addition, the boric acid-containing compound solution did not become a refractory and fireproof material because it does not form a solution due to a change in temperature and does not form a solution when dried.

A water-soluble product that does not use solvents and is a preservative and insect-proof material without generating harmful decomposition gas in case of fire. However, the well-known solubility (dissolution g / 100 water, 20 degreeC) of a boric acid compound has the weak point which is only about 5%, and it did not become a high concentration product.

As described in the present specification, the present inventors propose to prepare a high-concentration boric acid compound composition by adding at least one of a metal ion sequestrant and a wet-permeable surfactant, and adding a phosphate compound or silanol salt to warm it.

In the course of adding the mixture, it was found that the crystal form of the boric acid compound changed. That is, when the reaction solution was heated to a high temperature, it became an apparent transparent solution, but when observed under a microscope, it was found that the crystal form remained and caused precipitation when returned to room temperature.

Here, the inventors of the present invention have elucidated a means and a method for forming a stable aqueous solution of a high concentration of boric acid compound without precipitation or precipitation and at the same time forming an amorphous coating upon drying.

There is no heat-resistant improving agent which improves the heat resistance temperature of polyolefin-based, polyether, polyester-based or synthetic resins thereof, and commercializes it by blending a high heat-resistant material into a low heat-resistant material. For this reason, various grade products exist with the difference of the heat resistance of 10-20 degreeC.

In addition, there are flame retardants that are regulated or will be regulated in the future, but no pollution-free flame retardants have been found to replace them. In addition, there are insect repellents, fire retardants, and flavoring agents that generate decomposition gases at room temperature or when heated. However, there is a risk of environmental pollution caused by the generated gases. The boric acid compound is known to have insect repellent, anti-fog, anti-fog, and other actions, but it is necessary to make the boric acid compound a high concentration solution in order to make it universal.

In order to make the boric acid compound into a high concentration solution, the borax and boric acid crystals must be micronized to a nanomicron size to be colloidal or amorphous. Even when the boric acid compound was complexed with a metal ion sequestering agent and attempted to micellize with a surfactant, their crystal forms remained in solution, and it was found that problems such as precipitation and precipitation remain.

In addition, even if an acid is added, the crystal of a boric acid compound does not become refine | miniaturized but it coarsened in some cases. Even if the heating conditions were applied to them, it was difficult to maintain a high concentration solution at room temperature.

Physically, in combination with the above-described methods or alone, micronization was attempted with a colloid mill, but stable microcolloid liquefaction and amorphousness were also difficult. This shape is shown in the drawings of FIGS. 17-19 later.

On the other hand, in order to use a boric acid compound as a fireproof and fireproof material practically, the boric acid compound containing composition should have 100-300% solubility, and the dry film should become a flat plate or a coating film.

The inventors of the present invention considered that the method of flame retarding various materials may be solved by an endothermic action that delays thermal conduction without shielding and decomposing the heat-resistant coating film rather than deoxidizing with conventional pyrolysis gas.

MEANS TO SOLVE THE PROBLEM This inventor proposes in this invention that a boric acid compound containing composition can semi-inflammify and flame-retardant wood and a natural fiber. In this case, if the concentration is high solution, the injection amount is made less, the drying is faster and the productivity is higher. The above-mentioned means for flame-retardant synthetic resin is required to attach the solid content of the solution of the present invention to the synthetic resin surface or to powder the solution and to inject it into the synthetic resin. In order to do so, it is necessary to make the boric acid compound containing composition high concentration. In addition, since the boric acid compound-containing composition is a fireproof and fireproof material, it is a heat-resistant coating film and should not be decomposed at high temperatures. More endothermic effect is required.

That is, the crystalline boric acid compound should be made into a 100-300% solubility solution which cannot exist in the conventional establishment, and the crystalline is amorphized thereon and made into a fire-resistant coating film.

The present invention solves these problems.

(Summary of invention)

In the first invention proposed by the inventors, the boric acid compound is mixed in an aqueous solution of a metal ion sequestering agent or an aqueous solution of a wet permeable surfactant so as to have a solubility of not less than 5 g / 100 g of water at normal temperature, and the mixture is 60 It is a high-concentration boric acid compound characterized by obtaining by hydrothermal reaction above ℃.

In the second aspect of the present invention, the boric acid compound is mixed with an aqueous solution of a metal ion sequestering agent or an aqueous solution of a wet permeable surfactant so as to have a solubility equal to or higher than 5 g / water 100 g at room temperature, and the mixture is hydrothermally heated to 60 ° C or higher. It is made to react, and it is obtained by adding either or both of the silanol salt which has phosphoric acid or a siloxane skeleton further, The high concentration boric-acid compound characterized by the above-mentioned. In the third aspect of the present invention, a boric acid compound is mixed with an aqueous solution of a metal ion sequestering agent or an aqueous solution of a wet permeable surfactant so as to have a solubility equal to or higher than 5 g / water 100 g at room temperature, and a weakly acidic or weakly alkaline photoacid salt is added thereto. It is added, and this mixture is obtained by carrying out hydrothermal reaction above 60 degreeC, The high concentration boric-acid compound characterized by the above-mentioned. In a fourth aspect of the present invention, a boric acid compound is mixed with an aqueous solution of a metal ion sequestering agent or an aqueous solution of a wet permeable surfactant so as to have a solubility equivalent to or higher than 5 g / 100 g of water at room temperature, thereby weakly acidic or weakly alkaline mineral acid salt. The mixture is subjected to hydrothermal reaction at 60 占 폚 or higher to obtain a high concentration boric acid compound, which is obtained by adding either or both of silanol salts having a phosphoric acid or siloxane skeleton.

Moreover, the inventors etc. propose the fire prevention and fireproof composition containing the high concentration boric acid compound which concerns on any of said 1st-4th invention as 5th invention.

In the above, "normal temperature" means 20 degreeC. That is, the solubility of the boric acid compound "corresponding to 5 g / 100 g of water at normal temperature" means having a solubility exceeding solubility corresponding to 4.7 g / water 100 g at 20 ° C, which has been known in the art.

In addition, in the above, "hydrothermal reaction above 60 degreeC" is for increasing the solubility of a boric acid compound. It is known that when the temperature is set to 60 ° C or higher, borax becomes precipitated as an insoluble pentahydrate at 60 ° C or higher, and the present invention solves this problem, and a high concentration boric acid compound in which the boric acid compound does not precipitate even at 60 ° C or higher is known. It is for the purpose of providing. Furthermore, it is preferable that the temperature which makes a hydrothermal reaction be 60 degreeC-100 degreeC.

Moreover, the pH of a high concentration boric acid compound can be adjusted to 4-8 arbitrarily by adding one or both of the silanol salt which has a phosphoric acid or a siloxane skeleton in the above.

Moreover, the inventors propose the following fire prevention, fireproofing materials, and binder using the fire prevention and fireproof composition containing the high concentration boric acid compound which concerns on said 1st-4th invention.

1. A fire-resistant and fire-retardant material obtained by combining a method of fire- and fire-resistant containing any of the above-mentioned high concentration boric acid compounds with wood by combining the methods of atmospheric pressure injection, pressure injection or vacuum injection.

2. The fire-retardant and fire-retardant composition containing any of the above-mentioned high concentration boric acid compounds is mixed with any of the synthetic resin or the ladex with any of the isocyanate group or the zinc oxide, or the composition containing the isocyanate group or the zinc oxide, and the fiber Fire-retardant and fire-resistant materials obtained by coating or impregnating any of the products, wood chips, wood chips, paper products or inorganic sheet-like products, at room temperature or by heating and drying them.

3. A binder obtained by adding a thermosetting resin to a fire prevention / refractory composition containing any of the above-described high concentration boric acid compounds.

4. Fire-retardant and fire-resistant material characterized in that it is obtained by apply | coating quenching or injecting the fire prevention and fireproof composition containing the above-mentioned high concentration boric acid compound to a textile product, a paper product, or a wooden product, and drying.

5. A fire protection and refractory material characterized by applying or kneading, drying and high heat resistance a fire-retardant and fire-resistant composition containing any of the above-described high concentration boric acid compounds to a synthetic resin solid, a silicone resin, and a fluororesin surface.

6. Fire-retardant and fire-resistant material comprising impregnating an arson- or fire-resistant composition containing any of the above-described high concentration boric acid compounds into an inorganic or organic woven or non-woven fabric and making it into a pre-dried sheet or a dried sheet-mold compound.

7. Fire-proof and refractory composition containing any of the above-mentioned high concentration boric acid compound, mixed with any of carboxymethyl cellulose or carboxymethyl hydroxyethyl cellulose, impregnated in an inorganic or organic woven fabric or nonwoven fabric, and semi-dried. Fire-retardant and fireproof material made of a prepreg sheet or dried sheet mold compound.

The present invention is a method of preventing borax and boric acid (hereinafter referred to as "boric acid compound") at a high concentration of a known solubility or higher and preventing low temperature precipitation, and a metal ion sequestering agent (hereinafter referred to as "chelating agent"). A permeable surfactant (hereinafter, referred to as "surfactant") was used. The method of arbitrarily adjusting the pH of the solution was to share at least one or more of alkaline borax, boric acid, phosphoric acid, condensed phosphoric acid, phosphate or condensed phosphate. Although the boric acid compound is liquefied by ionizing the chelating agent or the surfactant, it is powdered when dried. MEANS TO SOLVE THE PROBLEM By mixing the silanol salt which has a siloxane skeleton, this inventor etc. could form a dry coating film without powdering. An alkoxide may be used instead of the silanol salt.

The present inventors made use of a chelating agent to adjust the solubility of the cement composition to be hydrated or to improve the solubility beyond the known solubility (for example, JP 44-4221 and JP 48). -40444). In addition, the inventors are Japanese Patent Application No. 48-24658, Japanese Patent Application No. 48-9681, Japanese Patent Application No. 49-25386 (Patent No. 1189741), and the following inventions. , Citric acid, ketocarboxylic acid, inosine acid or salts thereof. Furthermore, it has been clarified that fluoride, chromium, zinc, boric acid compounds, and phosphoric acid compounds also have mutually reinforcing effect with the chelating agent. In addition, surfactants having a chelate effect also have an effect of enhancing solubility by ionizing a water-soluble metal.

The chelating agent includes NTA, EDTA-OH, DTPA and other various sugar acids in addition to the above. The surfactant of the present invention includes an anionic surfactant or a hydrophobic group in which a hydrophobic group is composed of a chain bond containing only carbon or an element other than carbon. Polycyclic anionic surfactants using raw materials, and cationic surfactants consisting of alkylamine salts and quaternary ammonium salts also exhibited effective effects. The chelating agent of the present invention is not limited to the above-mentioned items, and the admixtures which increase the amount of dissolution beyond the well-known solubility in each temperature condition and make it a transparent solution can also be used in combination according to the regular method.

The silanol salt having a siloxane skeleton for coating the ion micelle dissolved in the present invention is an aqueous crude inorganic compound invented by the inventors, etc., and Japanese Patent Laid-Open No. 4-239079 and US Patent No. 5049316 and the corresponding Japan Japanese Patent Application Laid-Open No. 7-365 and Japanese Patent No. 7-14801. Material Technology Vol. 9, in 1991 or at EVALMAT, 1989, International Association of Steel Associations.

That is, a hydrated synthetic polymer composed of a mineral acid salt and an alkali metal, whether a metal (silicon, aluminum or other metal) or a mineral acid (sulfuric acid, phosphoric acid, boric acid, hydrofluoric acid, nitric acid or a sub-mineral thereof). Silanol salts using ammonia instead of photoacids are also within the scope of the present invention, and are used for shortening the residual salt time. Moreover, the said silanol salt is not limited, For example, alcohol-modified methyl silanol and an alkoxide can also be used.

The known solubility of borax 10 beard is only 4.7 g / 100 g of water at 20 ° C, and the solubility does not increase at 60 ° C to precipitate pentahydrate. Boric acid is 3.992 g / 100 g of water at 20 ° C. and 40.2 g / 100 g of water even at 100 ° C. (Rikaga Dictionary P. 1260-1261, 1976). That is, it was clear from the well-known solubility of boric acid and a borax that it does not become more than 5% solution concentration at 20 degreeC. Actually, the solid content of the synthetic resin solution of the commercially available binder is 45% by weight based on the total amount. For example, 45% is 45g / 55g, that is, 81.8% according to the solubility rate, but is practically used at a concentration of about 40%. This is 66.6% in terms of solubility of the boric acid compound.

The inventors tested whether the solubility of practical solid content 50g / water 100g (water) is possible below.

The dissolution test was carried out under the mixing conditions of 250 parts of boric acid 10 whiskers and 500 parts of boric acid 250 parts of the total amount of chelating agent or surfactant to 20 parts of water. The additive was added to water and warmed to 30 ° C. or higher, and then the borax and boric acid-containing mixture (hereinafter referred to as “boric acid containing compound”) was added to continue heating to an atmospheric maximum boiling temperature, and cooled to 20 ° C. to observe. The result was as follows.

Representative of the additives, oxycarboxylic acid is citric acid, oxyketone carboxylic acid is ascorbic acid, nitrogen compound sodium inosinate, ion blocking agent is ethylenediamine tetraacetate (EDTA), anionic surfactant sodium dodecylbenzene sulfonate ( F-25), sodium alkylnaphthalenesulfonate (NB-L) dialkylsulfosuccinate, sodium alkyldiphenylether disulfonate (SSL), special carboxylic acid type (ASK) naphthalenesulfonate formalin condensate sodium salt (NBL), special As aromatic sulfonic acid formalin condensate sodium salt (SS-L), special polycarboxylic acid type polymer (PS, 520), and cationic surfactant, stearamine acetate (86) and steardimethylammonium chloride (D86P) were used.

When either was used, it became a transparent solution under the above compounding conditions and maintained at a liquid temperature of 35 ° C. and precipitated slightly. In the total weight of the heated evaporation residue, hydration residue precipitation showed the highest amount of precipitation of about 25% with NBLASK at 20 ° C., but the other showed less than 15%, and the highest solubility of ketocarboxylic acid within about 10%. . That is, it became more than 33.8-43.1g / water 100g, well-known solubility. PH was shown before and after 7 at 20 degreeC, and even if it changed the blending ratio of borax and boric acid, pH was not adjusted arbitrarily in the range of 4-8.

Further, the solution was impregnated into cotton cloth to dry, i.e., powdered. However, when 10 weight part or more of emulsions are mixed, it will become a film and fire-resistant.

The present inventors applied the solution to the slide glass according to the mixing step of the additive in the test and observed the dry coating film. As an example of a chelating agent, the crystalline form of the case of using an anionic alkylnaphthalenesulfonic acid (NBL) and a cationic stearamine acetate (SAA) as an example of an oxyceltic carboxylic acid and surfactant is 80 degreeC in aqueous solution 500cc. It observed and maintained above. The result was made into a 25-times photograph by a microscope, and it expanded to 20 times and 500 times further with a video, and is shown in attached 17th-19th. FIG. 17 is a case where oxyceltic carboxylic acid is used, FIG. 18 is a case where alkylnaphthalenesulfonic acid is used, and FIG. 19 is a case where stearamine acetate is used.

In each figure, (a) is a case where 200g of borax (henceforth "BN") is mixed, (b) is a case where 2g of chelating agents and surfactant are mixed again in the state of (a). (e) is a case where 100 g of boric acid (henceforth "BA") is mixed, (d) is a case where 20 g of phosphoric acid (89% purity) is mixed again in the state of (c).

As a result of this observation, it was found that the crystalline became finer, the network became a bond, and the coating film.

Here, the inventors made further studies to make the crystalline of the boric acid compound amorphous, and to make a stable colloidal solution.

Although borax or boric acid alone or mixed to warm up and stirred until boiling at room temperature in order to form an aqueous solution, the crystal form was small but there was no basic shape change and could not be refined.

The chelating agents such as EDTA and NTA already proposed, oxycarboxylic acids such as citric acid or diketogluconic acid, inosinic acid having nitrogen or phosphorus, or anions, cations or neutral surfactants, ethylene glycol or polyether (PPG Boric acid compound was mixed in water mixed with PTMEG and PTG), stirred, warmed, and crystals of borax pentahydrate formed at 60 ° C or higher remained through a colloid mill.

Furthermore, even when borax sodium was added to phosphoric acid, sulfuric acid, or nitric acid to form a sodium salt, the crystal form was changed, but it was found that the crystals coarsened inversely depending on conditions.

From the above observations, there was a need for catalysis or coupling action to promote crystal change. Under the above conditions, an alkali metal salt of a weak acid or weak alkali, for example, sodium fluoride (pH 7.74), sodium phosphite (pH 7.02), sodium sulfite (pH 9.87), sodium nitrite (pH 9.04), sodium fluoride ( pH 6.2) was easily selected by mixing. Alkali metal can use all Na, K, and Li.

This dry coating film changed into a glass form or a film | membrane substance, and the crystal form of a boric acid compound was not found. As for the salt of the said chelating agent and surfactant, monovalent salt is preferable.

When 1-20 weight part of 85-89% phosphoric acid was added to the said mixture, pH could be adjusted to 4-8 arbitrarily and the low temperature precipitation also improved. Phosphoric acid used for this pH adjustment is not limited to regular phosphoric acid, Condensed phosphoric acid and these salts are included, In addition, it has an alkali chelate action effect of borax. The cotton cloth was soaked in these liquids and dried, that is, the film formation was somewhat improved.

As the chelating agent and the surfactant, boric acid and borax are dissolved in an ion micelle. It is considered. When the silanol salt which has the said siloxane skeleton was used for this binder, film formation property improved.

When 1-30 weight part of 20% liquids of the said silanol salt (Si, B, Na) whose mineral acid is boric acid were continuously mixed with phosphoric acid in the said mixing | blending, fire-resistance treatability improved. 100 g / m <^2> of glass nonwoven paper was immersed in the solution of this invention (henceforth "PHN") which mixed 5 weight part of said silanol salts with the said mixture, and dried.

The fire resistance was tested for the products which performed such a treatment and the untreated product. When a burner having a tip temperature of 900 ° C. was exposed to an untreated product, a hole was drilled for 1 to 2 seconds, but the treated product had a fire resistance of about 15 seconds.

The pH of the PHN solution was adjusted to 5.8, and 20% of the 60% concentration melamine resin was mixed to obtain a binder. 200 parts of newspaper pulp was mixed with 100 parts by weight of the binder, and heat-pressed at 140 ° C, that is, thermosetting without a curing catalyst.

When the silanol salt was blended in excess and mixed, a fibrous binder ceramic was obtained. On the other hand, when the photonic acid of the silanol salt is, for example, HNO ₂ (Si, No, Na), needle crystals were obtained.

In the above reaction, if only a high concentration solution was used, a high concentration solution of boric acid compound was produced even without addition of a phosphoric acid or other aqueous mineral film solution. One of the objectives is to make the solution of the present invention a fireproof and fireproof material. For this purpose, it must remain without decomposing at high temperature.

When the aqueous membrane-forming inorganic solution proposed by the present inventors was first added, the above-described boric acid compounds, surfactants, and high concentrations of boric acid compounds of mineral salts could be stabilized and refractory. The reason for its existence can be explained by the result of analysis by DTA-TG and FTIR.

Since the raw material of the solution of the present invention is borax before and after pH 9 and boric acid before and after pH 5, the pH of the resulting solution can be adjusted by the use ratio. The weight ratio is pH 7 or more when Na ₂ B ₄ O ₇ of the borax component exceeds H ₃ BO ₃ of the boric acid component, and pH 7 or less when the boric acid component is large.

The effect of this invention was confirmed by microscopic observation.

CAD-600 (manufactured by Kao Kagushi KK) of polydicarboxylic acid-based surfactant was added to 20 g / 1000 cc of water according to the above-mentioned blend, and 500 g of bora / boric acid were added to each glass and 250 g of boric acid was added. Calcite and monoclinic columnar crystals were interspersed. The dried material showed mass crystals. Subsequently, 50 g of phosphoric acid was mixed and stirred, that is, needle crystals were collected in a cluster shape using a boric acid compound as a nucleus. To this was mixed 100 g of a 7% solution of the silanol salt containing (Si, B, Na). Although the solution was transparent, it was observed by drying, that is, the crystal before mixing was changed to an amorphous glassy material, and the coating film state in which the nonwoven fabric was bonded to the fused random network was observed. According to other conditions, it changed into a four-phase crystal | crystallization, the leaf phase of a bank, and an oil-like crystal of a bank, and became a reticulated film bonding phase further.

That is, when borax and boric acid are added to the chelating agent of the present invention, an amorphous plate-like crystal is formed, and monophosphate is increased by the phosphoric acid, a model of a mesh bond is formed, and when the silanol salt is added, a melt-bonded synthetic resin The shape which formed the random bonding coating film like a nonwoven fabric was obtained by microscope observation.

The solution (PHN) of the present invention was injected into cedar wood. Kitchen House Co., Ltd., a wood injection device manufactured by Sato Iron Works, was used to inject a combination of normal pressure, high pressure, and pressure.

Since the boric acid compound PHN solution is a transparent solution, an injection amount close to the theoretical value of 280% of the weight of cedar wood is obtained. This was subjected to JIS fire prevention test, and the TDθ was only 100 and the CA was 6 in the 6 minute heating test.

That is, sufficient results which passed JIS flame retardant class 3 were obtained.

Hemp 5mm thick nonwoven fabric (manufactured by Dogo's Co., Ltd.) was immersed in a mixture of the boric acid-containing compound PHN and 60% melamine (sanwa Chemical Co., Ltd.) at a ratio of 80:20. The thermosetting was carried out at. The product was burned with a simple burner, but only carbonized without generating sparks. In the same way, after solidifying the newspaper fiber using the PHN solution as a binder, a fire protection test was conducted for 20 minutes, that is, a test result approximating to JIS flame retardant class 2 was obtained.

A mixture of 45% solution of latex made of 10% and 3% of special isocyanate was adjusted and added to a PHN solution, which was then applied to a cotton cloth, showing flame retardant effects without burning even when complexed, and at the same time washing resistance.

Thermosetting resin and sulfur can be used for the crosslinking agent of PHN and latex liquid mixture of this invention. In particular, methylated metyrolmelamine is effective.

Zinc is used in place of the isocyanate, coated on paper and cured at room temperature.

When the paper was made into a sheet of 1 mm of alumina silica, the weak defect of the tear of the sheet was improved to be nonflammable.

The known solubility of the boric acid-containing compound at 20 ° C. is about 5%, but according to the present invention, the solubility of 120 g / water or 100 cc is possible if the temperature is 70 ° C. or higher. The solution of borax has a pH of around 9 and the solution of boric acid has a pH of around 5, but the present invention has the effect of arbitrarily adjusting the pH to 5-8.

In addition, the present invention provides a high-concentration transparent liquid containing a boric acid-containing compound, which can be injected into a 1-micron conduit of wood, and by drying the film, a single injection drying process that has not been possible until now, the wood has a natural color and a substrate. It has the effect that can be obtained by retaining JIS flame retardant 2-3 grade. Impregnation of the solution of the present invention results in flame retardation of natural products such as paper, cotton and hemp products, and heat-resistant reinforcement of glass, rock wool and inorganic fiber products. In addition, the high-concentration solution of the present invention becomes a flame retardant product which does not generate combustion gas or smoke because the binder of flame retardant chip board, particle board, MDF, and lump molded product is made of a binder like synthetic resin.

Further, as a result of the following improvement, a boric acid compound having a high solubility of 100 to 300%, which was impossible in the prior art, could be produced.

Even when a chelating agent or a surfactant was added to the water and stirred, it was found that sufficient effect was not produced unless it was dispersed in a uniform colloidal phase. It has been found that the above-mentioned weak alkali or acidic sodium fluoride, sodium phosphite, sodium sulfite, sodium nitrite and sodium borofluoride have a function of dispersing colloidally by adding less than half its weight to a chelating agent or a surfactant. . They are added to the weak acid or weak alkali before the chelating agent or the surfactant, and then borax is added to the glass film. After the addition of the chelating agent, the surfactant and the borax, or at the same time, the addition of the weakly acidic or weakly alkaline substance to boric acid further changes the crystal of the boric acid compound on the coating film.

By this action, a high concentration solution having a solubility of 100 to 300% of the boric acid compound that has not been possible until now can be realized.

The aqueous film-forming inorganic compound proposed by the present inventors is a silanol salt, but the fire-bonding property is generated only by adding it to the boric acid compound of the present invention (addition of 5% or more solid content of the boric acid compound). It is probably considered based on the coupling action.

Cedar 15mm × 200mm × 300mm was put into a tube filled with PHN 40% liquid (NF-MH) of the present invention, depressurized, pressurized at 20kg / cm ² , and dried at an injection rate of 630 liters / m ³ . It was confirmed that the solid residue was 250 kg / m ³ , and the quasi-non-combustible test was carried out with a fire tester made by Toysei Seiki. Results of TDθ 37, CA 6, and Af of 18 seconds were obtained.

In addition, when 0.1% or more of carboxymethyl cellulose (CMC) or carboxymethyl hydroxyethyl cellulose (CMHEC) was added, thermal bond resistance was generated despite being an organic substance.

1g CMC was added to 125g / cm ² hemp fiber and 20% of the PHN (NF-MF) was applied and dried.

Even if burned by the burner of the tip 1000 ℃, it became red by the fire but did not penetrate.

A thermosetting resin such as urea resin, melamine resin or phenol resin can be freely mixed and used in the solution of the present invention.

Therefore, the solution of the present invention is impregnated with glass fiber or carbon fiber (not limited to these), used in combination with the completely inorganic or the above-mentioned thermosetting resin, and made into a pre-flag sheet in an unreacted state that leaves moisture. Could.

Since the film-forming substance of the present invention described above has a B-O (late FTIR) reactor, it has a mixing property with a synthetic resin having an ether and ester bond, and has heat resistance and endothermic action, thus becoming a flame retardant material completely different from the conventional one. The moldability of the dried resin was mixed with PP (Mitsui Seki Oil Co., Ltd.) and the present invention solution PHN (NF-MF) at a 30% solids concentration (toyo test rabomil test results). In addition, the flame-retardant HB test showed that the present invention had a heat resistance of 5 minutes 10 seconds with respect to 1 minute 50 seconds. Moreover, when 50 weight part of solid content of the said PHN article of this invention was penetrated with respect to PP, the HB test became 6 minutes and 30 second.

It also worked effectively for the olefin system which was considered difficult in the past.

This was extruded into a sheet, made of glass cross and laminated, and formed into SMC, and the helmet was hot press formed from the sheet.

It demonstrates in an Example below.

(Example 1)

Grade Borax 10 beard and boric acid and 89% phosphoric acid (made by Daihei Chemical Co., Ltd.) with a purity greater than or equal to 99% made in the United States were tested. EDTA 2Na was selectively added and dissolved in 5 g, 10 g, 20 g, 30 g, 40 g, and 50 g in 1000 cc of water, and the mixture was heated to 30 ° C to 60 ° C. A total of 250 g of borax and boric acid, respectively, were mixed. As 5 g of EDTA mixing amount, even if there were remainder undissolved at 30 degreeC, it melt | dissolved fully when it became 80 degreeC or more.

Also in the amount of other additions, the remainder undissolved at 30 deg. C decreased, but completely dissolved at 60 deg. However, as the liquid temperature lowered to 35 ° C. or lower, precipitation started, causing 10% of the total weight, which is the highest precipitation at 20 ° C., to precipitate. That is, solubility of 35 g / 100 cc or more was obtained. It heated up again and needed 70 degreeC or more to be converted.

(Example 2)

The same experiment was conducted using the chelating agent of Example 1 for citric acid, ascorbic acid (ketocarboxylic acid) and sodium inosinate of oxycarboxylic acid. Although melt | dissolved at 75 degreeC or more, 15-25 weight% precipitated at 20 degreeC. That is, it became more than 13-28 g / water 100cc and well-known solubility.

(Example 3)

The same experiment was performed using the following anionic surfactant or cationic surfactant instead of the EDTA of Example 1.

As an anionic surfactant, SS-40N (fatty acid salt, product made by Kao Corporation), Emar group (alkyl sulfate ester), Neoperlux 25 (sodium dodecylbenzene sulfonate), Perex NB-L (sodium alkyl naphthalene sulfonate), Fepex OT-P (sodium dialkylsulfosuccinate), Ferex SS-L (sodium diphenyletherdisulfonate), lattemur WX (sodium polyoxyethylenealkylether sulfate), lattemur ASK (special carboxylic acid anion) , Demole NL (β-naphthalene sulfonic acid formalin condensate sodium salt), Demole SS-L (special aromatic sulfonic acid formalin condensate sodium salt), Demole EP Poise 521 (special polycarboxylic acid polyanion), methylene Glycol and polypropylene glycol were used.

Acetamine 86 (stearamine acetate), coyne 24P (lauryltrimethylammonium chloride) and mannitol 24B (laurylbetaine) were used as the cationic surfactant.

In either case, the solubility of 50 g / water 100 g or more was obtained even if the mixture of boric acid and borax was known from 60 degreeC or more to 90 degreeC.

However, below 20 degreeC, 20-25% of precipitation of the total weight generate | occur | produced.

(Example 4)

The special polycarboxylic acid surfactants WH-Z and CAD-600 made by Kao Kagaku Co., Ltd., which are used for the cement admixture, were used separately from the EDTA of Example 1 above. There was about 10% undissolved precipitation of the boric acid compound at 50 ° C., but 50 g (5% of water and 10% of boric acid compound) of 89% phosphoric acid was dissolved.

(Example 5)

An experiment showing the solubility of 1000 g of borax / 1000 g of water was attempted using the polydicarboxylate CAD-600 used in the above examples. 100 g of the ratio of 10% / borax in CAD-600 was mixed with water, and warmed to 60 ° C, resulting in undissolved residues of borax pentahydrate.

100 g of 89% phosphoric acid used in the above example was added and mixed, that is, a transparent solution was obtained.

Slight aggression was found at 20 ° C. Precipitation later occurred.

(Example 6)

The "cement admixture consisting of special hard gypsum" according to the invention of Patent No. 1189741 fired a dihydrate gypsum mixed with 1 g of calcium fluoride and 100 g of gypsum at 750 ° C., but has a dissolution promoting effect. In place of 20 g of EDTA in Example 1, 10 g of the pumice gypsum (CaF ₂ / boric acid compound = 0.02%) and 2 g of citric acid (2 g / 500 g, 0.4%) were used as a chelating agent. That is, the boric acid compound heated up at 80 degreeC dissolved.

(Example 7)

It becomes solubility of 70 g of boric acid containing compounds / 100 g of water, and at the same time, adjusts pH arbitrarily to 5.5-9, and shows the implementation process which consists of transparent solutions below.

300 g of the above-mentioned special polycarboxylate maithi-WH-Z made by Kao Kagaku KK was mixed with 10 kg of water. pH was 8.85.

1.2 kg of borax 10 whisker of the above 99% purity was mixed thereto. pH was 8.9.

Even if it warmed at 50 degreeC, there existed undressing residue.

500 g of 89% phosphoric acid was mixed. pH became 4.98 at 68 degreeC, and undissolved residue disappeared.

500 g of the silanol salt 23% liquid which has the siloxane skeleton of the (Si, B, Na) elemental composition by the Corporation Co., Ltd. was mixed here, ie, it became a transparent liquid, pH was 5.27 at 56 degreeC.

While heating was continued, 2 kg of crude 99% boric acid was mixed to pH 3.12 at 72.8 ° C., and 500 g of boric acid was further mixed to pH 3.08. 3.3 kg of said borax which shows alkalinity was mixed, and pH was set to 5.38. It was transparent above 50 degreeC.

It became the solubility solution of 70 g of boric acid containing compounds / 100 g of water.

(Example 8)

By the solid content measurement method of 105 degreeC * 3 hours heating, # 130 which becomes solid content 20% or more and # 140 which becomes 30% or more of solid content were adjusted, heating up to 80 degrees C or less by the following combinations.

In the said compounding example, pH could be easily set to 4 by increasing phosphoric acid. To increase the pH, the borax ratio may be increased in the ratio of borax / boric acid, and pH 7 and 9 may also be adjusted. Phosphoric acid is not limited to regular phosphoric acid, and the same pH adjustment results were obtained even when condensed phosphoric acid was used. That is, the pH was freely set by changing the blending ratio of borax, boric acid and phosphoric acid.

For each of the clear liquids (# 130 and # 140) obtained above, the crystal structure was observed by a 25-fold photograph by a microscope and again by a 20-fold system by 500-fold video (Fig. 20 (a), ( b), (c), (d)). (a) is a state in which # 130 is an amorphous coating film, (b) is a state in which # 130 is injected into a wood and applied to the tissue surface, (c) is a state in which a # 140 is an amorphous coating film, (d) is # 140 is injected into wood and shows the state applied to the surface of the tissue.

Using the above-mentioned clear liquid, wood injection experiment was attempted.

* Used equipment Sato Iron Works 0.6m diameter × 4m

* The ubiquitous specific gravity of wood Kanayama cedar 0.358 water content 11.5%

It was dried at 60 ° C. for 48 hours. There was no modification.

The test specimen had a natural substrate, no discoloration, and was beautiful.

On this specimen, the test results of the surface test specified in No. 3415 of the construction notice shall be displayed.

(Example 9)

Solid content of # 130 of the said Example was 21.2% by the measurement of 105 degreeC x 3 hours. When 80 parts of this mixture and 20 parts of 60% melamine (Sanwa Chemical Co., Ltd.) were mixed, the solid content became about 30% of each. A 7 mm hemp nonwoven fabric (manufactured by Tosko Corp.) was immersed in the PHN solution, the excess was dehydrated, and thermoset at 130 ° C.

The used surfactant had a carboxyl group and was cured in 10 minutes without a catalyst.

In the same fire retardant test as in the above example, test results of passing JIS flame retardant class 3 were obtained.

Even if the solution was diluted twice with water, immersed and dried in the same manner, a test result that passed the JIS flame retardant class 3 test was obtained.

Example 10

1 kg of newspaper pulp (made of tithing paper) was immersed in the PHN-melamine mixture of Example 9, and the surplus was centrifuged to give pulp: mixed solution = 1: 2. It was heated at 150 ° C. for 10 minutes and thermoset molded. In Nippondetsu Shayogikai Kijutsukyokai, the alcohol burning test was 15mm thick, but the carbonization length was 85mm below the specified 100mm without ignition, ignition, debris, and dust, and the test result was equivalent to nonflammable materials.

(Example 11)

A 10 mm thick product of Sambu Woven Fabric (manufactured by Tosko Corporation) was diluted twice with water by diluting the PHN-melamine mixture solution of Example 9 with water, and the resultant was squeezed to give 3: mixture solution = 100: (350 to 400).

It was dry cured at 130 ° C. Although there was a flexible phase in white, carbonization was carried out even if the welding melting flame fell, but there was no complexing or permeation.

Example 12

Each of acrylic, styrene, and rubber latexes (additives) was added to the solution made of urea resin in the melamine of Example 9, 1% of the zinc mixture was further mixed, and 1% of the zinc mixture was mixed to adjust three kinds of liquids. . This was immersed 100g / m ² cotton cloth.

After drying, it was treated with the isocyanate isocyanate. Even if it was washed with a washing resistance and a burner, flame retardancy without complexation was obtained.

(Example 13)

10 g of EDTA 40% liquid was mixed with 500 cc of water, and the mixture was heated to 80 deg. This was taken as a 25-times photograph by a microscope, 20 times in a video, and 500 times in a system, ie, it did not become uniform dispersion (FIG. 21 (a)). To this was added 3 g of sodium fluoride (manufactured by Hasimodo Kasei, hereinafter referred to as "NF"), stirred, and dispersed uniformly (FIG. 21 (b)). 230 g of borax 10 whisker (99% purity made in USA) was added thereto, and stirring was continued while heating, that is, the crystals were flattened randomly (Fig. 21 (c)). Further, 135 g of boric acid (99% purity made in USA) was added, and stirring was continued, that is, its dry coating film was formed into a glass, and no crystal was found (Fig. 21 (d)).

30 g of a 7% solution of silanyl fluoride salt (manufactured by Co., Ltd., hereafter referred to as "MF") prepared from metal silicon, sodium fluoride, and sodium hydroxide was added thereto, ie, precipitated at room temperature (20 ° C). There was no precipitation (Fig. 21 (e)).

In this 20 degreeC state, pH was 7.2.

The same observation was performed using NBL instead of the said EDTA.

In the same step as above, the same micrographs were taken and examined.

This is shown in Figs. 22 (a), (b), (c), (d) and (e).

Example 14

The solution of Example 13 was dried to 5% moisture at 150 ° C and powdered, and the result of analysis (hereinafter referred to as "NF-MF") was obtained at 20 ° C, 400 ° C, and 800 ° C by DTA-TG and FTIR. 1 to 4 are shown.

With DTA-TG, even if it is 800 ℃, the weight change is small and the endotherm is continued. In FTIR, water molecules around 3450cm ^-1 do not lose their heat even when heated to 800 ℃, and they have an endothermic effect, and are near 1400cm ^-1 . The BO vibration of was changed by heating, but silanol groups around 1065cm ^-1 remained undissolved even at high temperature.

In other words, the fire-retardant and fire-retardant required the above-described fluorinated silanol salt (aqueous film-forming inorganic compound).

Example 15

The sodium fluoride of Example 13 was replaced with sodium phosphite (hereinafter referred to as "NP"), sodium nitrite (hereinafter referred to as "NO"), sodium sulfite (hereinafter referred to as "NS"), and the above-described silanol salt (MF). Phosphoric acid (Si, P, Na) (hereinafter referred to as "MP"), nitrates (Si, NO, Na) (hereinafter referred to as "MO"), and sulfuric acids (Si, S, Na) (hereinafter referred to as "min") DTA-TG and FTIR in the case of using "MS" were observed in the same manner as in Example 14.

The results are shown in FIGS. 5 to 16.

In either case, the weight loss was small without decomposition at 800 ° C or higher, and the peaks of hydroxyl and silanol groups remained strong. This compounding can be regarded as the same action as the case of adding sodium borate fluoride in terms of chemical composition.

Example 16

In the above example, if the surfactant or chelating agent is 15 g of borax and 10 g of boric acid, 0.3 g of 1% or more of the boric acid compound is present, and at the same time, 0.25 g of the mineral acid salt is 0.25% or more of the boric acid compound, even if the silanol salt is lacking. The solubility of the compound became a transparent solution of boric acid compound of 5 g / 100 g or more.

(Example 17)

To 500 cc of water, 250 g of borax, 250 g of boric acid, 20 g of sodium dodecylbenzenesulfonate, and 5 g of sodium phosphite were combined and heated to 80 ° C. or higher by the above method to obtain a clear liquid. Solubility was 100%. Furthermore, the dryer was set to 120 degreeC, it dried for 3 hours, and it was set as 5% of moisture. It could be micronized to 200 mesh or less by a ball mill. Powder of solubility of boric acid compound = 500/250 + 250 = 100% could be easily prepared.

(Example 18)

Experimental results of 200% (200g / 100cc water) of boric acid compound are shown.

45 g of polyethylene glycol maleate of a surfactant was mixed and stirred in 500 g of water, heated to 85 ° C, 600 g of borax was added, and heating was continued while adding 25 g of sodium fluoride.

400 g of boric acid was added thereto, followed by high speed mixing. It became transparent solution when it became 80 degreeC or more. Even if no mineral acid was added, the solution became a high boric acid compound solution (1.000 g / 500 g water) having a pH of 6.93 and a specific gravity of 1.37, and was maintained at 20 ° C. without precipitation and precipitation. After a few days, however, a solidification occurred on the inner wall of the poly container. On the other hand, 100 g of a 15% solution of silanol salt of MH type of (Si, BH ₃ , K) was mixed with a high-speed stirring solution to the above-mentioned solution at 80 ° C and made clear. This solution was a clear solution even if stored for a long time (30 days).

Example 19

In Example 18, a representative chelating agent of the surfactant, NTA, Na ascorbic acid, sodium anionic dodecylbenzene sulfonate (F-25) of the surfactant, sodium alkyl naphthalene sulfonate, and cationic steardimethylammonium chloride, neutral Although propylene glycol and ethylene glycol were mixed and used, there was no problem.

Example 20

A 125 g wound sheet of hemp fibers (manufactured by TOSCO Co., Ltd.) was added to a NO-MO solution of 20% boric acid compound solids, and 1% of carboxymethyl cellulose (CMC) (first Kogyo Seiko Pharmaceutical Co., Ltd.) was added. It was put in the tank of Nippon-Enshi Co., Ltd.), and it immersed at the speed of 10m per minute, squeezed with a roll, and dried at 120 degreeC.

The test result (the test result in Kanagawa Ken Gijutsu Shiken Center) of the combustibility test method A-2 (Meckel burner method) of the textile product

This was. It corresponds to a noncombustible material.

Nippon Paper wallpaper also obtained the results of zero residue and zero residue.

Example 21

In Example 13, the following combinations (shown by abbreviation) were tested.

Sodium fluoride (NF), sodium phosphite (NP) sodium sulfite (NS), sodium nitrite (NO)

When the above-mentioned thing is used for the mineral acid of silanol salt (water-based inorganic film-forming compound),

Sodium fluoride (MF), silanol borate (MH), sodium phosphite (MP), sodium sulfite (MS), sodium nitrite (MO), with the formulation of Example 13, the solution of the present invention was started. .

NF-MF, NP-MP, NS-MS, NO-MO, NF-MH, NP-MH, NO-MP, NS-MH, etc., were freely combined, but in any case, it became a transparent solution at 20 ° C. Did not occur.

The solution was taken in slide glass and dried.

In either case, the crystalline form of the boric acid compound was lost and became a flat plate or a coating film.

Example 22

A solution of pH 6.9, specific gravity 1.45, and a 200% solubility of boric acid compound was obtained under a compounding condition of 500 cc of water, 20 g of sodium polyacrylate, 600 g of borax, 5 g of sodium fluoride, 400 g of boric acid, and 100 cc of silanol borate (MH).

The solution was kept at 80 ° C. and immersed in ABS, polyester, PP and PE. It was dried and the process which made about 40% of solid content adhere.

PP and PE were flame retardant (HB) for 2 minutes of untreated material, and the treated material was flame retarded for 7 minutes or more.

ABS and polyester obtained the result of V-O by the UL flame retardant test.

Example 23

An example of 300% solubility of the boric acid compound is shown below.

30 g of sodium polyacrylate and 20 g of sodium phosphite were added to 500 cc of water, and the mixture was heated to 90 ° C. While heating was continued (maintaining 90 ° C.), 1000 g of borax was mixed with gentle stirring. Then 50 g of 89% phosphoric acid was added. High speed mixing made it almost transparent. Subsequently, 500 g of boric acid was added, followed by high speed stirring. Continued heating became transparent (while maintaining 90 ° C). 100 g of MP (silanol salts (Si, P, Na) using phosphoric acid as a mine) was added thereto, and heating and stirring at 90 ° C were continued for 5 minutes, and the process was finished. When the liquid temperature of a solution fell to 20 degreeC, this solution was observed, ie, it was a transparent state.

Example 24

As the surfactant, sodium polyacrylate (PS 521 manufactured by Kao Kagushi KK) having a function of a chelating agent is used. 5 g of the above sodium polyacrylate (PS 521) was added to 500 c of water, 230 g of borax and 140 g of boric acid were mixed, and further, 3 g of sodium fluoride was added to warm to 80 DEG C. Then, 30 g of a 7% solution of silanol salt (MF) was added. Was added. The solution was taken on a slide glass and observed, that is, a smooth coating film and no crystalline form was found.

As above, sodium polyacrylate (PS 521) is used.

5 g of sodium polyacrylate (PS 521) was added to 500 cc of water, 230 g of borax was mixed, followed by neutralization by addition of 20 g of condensed phosphoric acid (85% reagent), followed by 3 g of sodium fluoride, 140 g of boric acid, and silanol salt (MF). 30 g of 7% solution of was added, and heating was continued. The heating was terminated at 90 ° C, the liquid was taken on a slide glass and observed, that is, as described above, a smooth coating film was found, and no crystalline form was found.

(Example 25)

15 g of carboxymethyl cellulose (CMC) was added to a solution of the present invention of the NF-MF type described in Example 13 and having a solubility of 150% of a boric acid compound, followed by uniform mixing and stirring. A glass cloth of 200 g / m ^{2 made} of Japanese glass neck was immersed in this mixed solution, placed on a polyethylene film, and semi-dried. The polyethylene film was further covered thereon and left to stand for 7 days.

Thereafter, the resultant was dried for 30 minutes at 120 ° C. and cured, that is, 60 g of solid content adhered.

Even if this hardened | cured material was burned with the burner of 1000 degreeC of a tip flame, it did not melt | dissolve or penetrate.

As a solution of the present invention of the above-mentioned NF-MF type, a boric acid compound and a solubility of 150% were mixed with 25% melamine urea resin in a weight ratio to obtain a mixed solution.

Using this mixed solution, the glass cross was treated as above and left to stand for 7 days, after that, it was heated at 150 degreeC for 10 minutes, and the thermosetting body was obtained.

As the solution of the present invention, the solubility of the boric acid compound was changed from 20% to 150% to obtain various kinds of noncombustible rejected products (JIS standard, TDθ0 by heating for 20 minutes).

Example 26

As a solution of the present invention of the NF-MF type described in Example 13, a 30% solubility of a boric acid compound was dried at 150 ° C for 6 hours, solidified and ground to a powder around 50 microns. 200 weight part of this powder and 100 weight part of plasticizers were mixed, and the mixture was obtained. 100 parts by weight of this mixture, 300 parts by weight of polyvinyl chloride (PVC), 6 parts by weight of a tin-based stabilizer, and 200 parts by weight of glass chips were mixed to form an SMC sheet with a roll of 3 mm thickness. The UL flame retardant test was conducted on the SMC sheet, and it was confirmed that the product had a self-extinguishing property of a grade of V-O. In addition, it was confirmed that smoke and chlorine gas were significantly reduced during the combustion test.

The SMC sheet could be molded into a helmet at 180 ° C.

Example 27

A solution of the present invention of the NF-MF type described in Example 13 and having a solubility of 100% of the boric acid compound were dried at 105 ° C for 3 hours. As a result of measuring the dried product thus obtained, it was confirmed that it had a solid content of about 36%.

The dried product and the polycarbonate having the solid content of the above 36% were mixed at the same weight and dried to obtain a resin to which the present invention adhered.

In the same manner, ABS, saturated polyester, polystyrene, and the dried product having the solid content of 36% were mixed and dried at the same weight to obtain resins to which the present invention adhered.

The four kinds of resins thus obtained were subjected to processing test with Toyosei's test labomil, that is, no abnormality at all.

Using these four types of resin as a test piece, it was confirmed that the flame retardant test (UL-V) was performed, that is, a grade product of V-O. Moreover, generation | occurrence | production of the decomposition gas and smoke by heating was able to be made few, without using the conventional flame retardant at all.

Example 28

A solution of various high concentration boric acid compounds described in the above examples was dried to obtain a product having a solid content of 10% or more. This product was gelled by mixing with Povar, latex. It was confirmed that the remaining product which squeezed excess water from this gelation became a flame-retardant product which has self-extinguishing property.

In addition, when 1-10% of zinc oxide was added to this gelled product, rubber elasticity occurred.

(Example 29)

The example of the solution of this invention which does not freeze also in the winter system is shown below.

The solution of the present invention was prepared using polypropylene glycol (PPG) and polyethylene (PE), that is, it did not freeze at 5 ° C or 0 ° C.

Preparation of the solution of this invention was performed with the following four examples.

The mixing | blending was mix | blended in the mixing | blending procedure shown on the left by weight g and each mixing example.

In the case of each compounding example, the temperature was made to hydrothermally react as 80 degreeC.

After completion of the reaction, it was confirmed that no precipitation was maintained for 10 hours in a refrigerator at 5 ° C., and further maintained at −5 ° C. for 5 hours, but no precipitation occurred.

1 is a diagram showing the results of differential thermal analysis (DTA-TG) for the present invention by the combination of sodium fluoride (NF) -silanol fluoride salt (MF),

2 is a view showing the FTIR at room temperature (20 ℃) for the present invention analyzed in FIG.

3 is a view showing FTIR at 400 ° C for the present invention analyzed in FIG. 1,

4 is a view showing the FTIR at 800 ° C for the present invention analyzed in FIG.

FIG. 5 is a diagram showing the results of differential thermal analysis (DTA-TG) for the present invention by combining sodium phosphite (NP) and a mineral acid of silanol salt as a mine (MP) using sodium phosphite;

6 is a view showing FTIR at room temperature (20 ° C) for the present invention analyzed in FIG.

FIG. 7 is a diagram showing FTIR at 400 ° C for the present invention analyzed in FIG.

FIG. 8 is a view showing FTIR at 800 ° C. for the present invention analyzed in FIG.

9 is a diagram showing the results of differential thermal analysis (DTA-TG) of the present invention by a combination in which the mineral acid of sodium nitrite (NO) and silanol salt is a mineral acid (MO) using sodium nitrite,

10 is a view showing the FTIR at room temperature (20 ℃) for the present invention analyzed in FIG.

FIG. 11 is a diagram showing an FTIR at 400 ° C for the present invention analyzed in FIG.

FIG. 12 is a diagram showing FTIR at 800 ° C for the present invention analyzed in FIG.

13 is a diagram showing the results of differential thermal analysis (DTA-TG) for the present invention by combining sodium sulfite (NS) and silanol salt as mine (MS) using sodium sulfite;

14 is a view showing the FTIR at room temperature (20 ℃) for the present invention analyzed in FIG.

FIG. 15 is a diagram showing an FTIR at 400 ° C for the present invention analyzed in FIG. 13;

FIG. 16 shows the FTIR at 800 ° C. for the inventive product analyzed in FIG. 13;

FIG. 17 is a view showing the change in crystal form in the mixing step of a boric acid compound and a chelate agent (oxyceltic carboxylic acid), (a) when 200 g of BN is mixed,

(b) is a figure which shows the case where (a) mixes surfactant further, (c), (c) mixes 100 g of BA, (d) shows the case where phosphoric acid was further mixed with (c),

18 is a view showing the change of crystal form in the mixing step of the boric acid compound and a surfactant (alkylnaphthalenesulfonic acid), (a) is 200g of BN is mixed, (b) is a surfactant and the like in (a) When mixing, (c) is a figure which shows the case where 100 g of BA are mixed, (d) is a case where phosphoric acid was further mixed with (c),

FIG. 19 is a diagram showing the change of crystal form in the mixing step of a boric acid compound and a surfactant (stearic amine acetate), (a) when 200 g of BN is mixed, (b) is a surfactant or the like in (a) When mixing, (c) is a figure which shows the case where 100 g of BA are mixed, (d) is a case where phosphoric acid was further mixed with (c),

20 is a view showing the crystal state of the invention (# 130) with a solid content of 20% or more, and the invention (# 140) with a solid content of 30% or more, and (a) is an amorphous coating film of # 130. The state, (b) is the state which apply | coated wooden fabric # 130, (c) is the state which made # 140 the amorphous coating film, (d) is a figure which shows the state which applied wooden fabric # 140.

21 is a view showing the change of crystal form in the production step of the present invention of the NF-MF type, (a) is a state in which EDTA is mixed with water, (b) is a state in which NF is mixed with (a), ( c) is a diagram showing a state in which borax is mixed in (b), (d) is a state in which boric acid is mixed in (c), and (e) is a state in which MF is further mixed in (d).

Fig. 22 is a view showing the change of crystal form in the production step of the present invention of the NF-MF type, (a) is a state in which NBL is mixed with water, (b) is a phase in which NF is mixed with (a), ( c) is a figure which shows the state which mixed borax in (b), (d) the state which mixed boric acid in (c), and (e) is the state which mixed MF further in (d).

Advantageous Effects of Invention The present invention provides a high concentration boric acid compound which can be formed in a high concentration aqueous solution with a stable solubility of 100 to 300%, at room temperature (20 ° C), without precipitation or precipitation, and can be formed into an amorphous coating upon drying. can do. Moreover, according to this invention, pH of the aqueous solution of a high concentration boric acid compound can be adjusted arbitrarily in the range of 4-8.

According to the present invention, a fire and fire resistant material containing a high concentration of boric acid compound can be used effectively and natural resources such as wood and natural fibers can be effectively used to provide an elegant fire and fire resistant material to the global environment without pollution.

Claims (12)

The boric acid compound is mixed with an aqueous solution of a chelating agent or an aqueous solution of a surfactant so as to have a solubility equal to or higher than 5 g / 100 g of water at room temperature, and the mixture is obtained by hydrothermal reaction at 60 ° C or higher. compound. The boric acid compound is mixed with an aqueous solution of a chelating agent or an aqueous solution of a surfactant so as to have a solubility equal to or higher than 5 g / 100 g of water at room temperature, and the mixture is subjected to hydrothermal reaction at 60 ° C or higher, and further, a phosphoric acid or siloxane skeleton is added. The high concentration boric acid compound obtained by adding either or both of the silanol salts to have. To the aqueous solution of the chelating agent or the aqueous solution of the surfactant, the boric acid compound is mixed so as to have a solubility equal to or higher than 5 g / 100 g of water at room temperature, and a weakly acidic or weakly alkaline mineral acid salt is added thereto, and the mixture is 60 ° C or higher. High concentration boric acid compound, characterized in that obtained by the hydrothermal reaction. To the aqueous solution of the chelating agent or the aqueous solution of the surfactant, the boric acid compound is mixed to have a solubility equal to or higher than 5 g / 100 g of water at room temperature, and a weakly acidic or weakly alkaline mineral acid salt is added thereto, and the mixture is heated to 60 ° C or higher. A high-concentration boric acid compound, which is obtained by subjecting to hydrothermal reaction and further adding either or both of a silanol salt having a phosphoric acid or siloxane skeleton. A fire prevention and fireproof composition comprising the high concentration boric acid compound according to any one of claims 1 to 4. Fire-proof and fireproof composition obtained by impregnating wood by combining the method of atmospheric pressure injection, pressurization injection or reduced pressure injection containing the high concentration boric acid compound of any one of Claims 1-4, and drying it. fire. Fire-retardant composition containing the high concentration boric acid compound of any one of Claims 1-4 is mixed with any of synthetic resin or latex, and isocyanate group or zinc oxide, or the composition containing an isocyanate group or zinc oxide, Fireproof and fireproof materials obtained by coating or impregnating any of textile products, wood chips, wood chips, paper products or inorganic sheet-like products and drying them at room temperature or by heating. A binder obtained by adding a thermosetting resin to the fire prevention / refractory composition containing the high concentration boric acid compound of any one of Claims 1-4. A fireproof / fireproof material obtained by drying, after coating, immersing or injecting the fireproof / fireproof composition containing the high concentration boric acid compound of any one of Claims 1-4 in a textile product, a paper product, or a wooden product. A fireproof / fireproof material comprising the fireproof / fireproof composition containing the high concentration boric acid compound of any one of claims 1 to 4 applied to a surface of a synthetic resin, a silicone resin or a fluororesin, or kneaded, and dried to high heat resistance. A fireproof / fireproof composition containing the high concentration boric acid compound of any one of claims 1 to 4 is impregnated into an inorganic or organic woven or nonwoven fabric, and the semi-dried preflag sheet or dried sheet mold compound is characterized by Fire and Refractory Materials. A fire-proofing and fire-resistant composition containing the high concentration boric acid compound of any one of Claims 1-4, and any of carboxymethyl cellulose or carboxymethyl hydroxyethyl cellulose are mixed and impregnated in an inorganic or organic woven or nonwoven fabric, A fire-retardant material comprising the semi-dried preflag sheet or dried sheet mold compound.