JPH0873212A - High concentration boric acid compound and composition for fireproofing/fire resisting use containing the same and binding material and fireproof/fire resistant material using the same - Google Patents

Abstract

PURPOSE: To convert wood and natural fiber into durables and also to use these as a pollution-free fireproof/fire resistant material. CONSTITUTION: A high concn. boric acid compd. is obtained by mixing a boric acid compd. to either aq. soln. of a metallic ion sealing agent or aq. soln. of a wet permeable surfactant so that a concn. of the compd. may be more than a solubility equivalent to 5g/100g water at normal temp., and subjecting this mixture to a hydrothermal reaction at >=60 deg.C or, moreover, adding either or both of phosphoric acid and a silanol salt having siloxane skeleton. And the fireproof/fire resistant material is produced by using a composition for fireproofing/fire resisting use containing the high concn. boric acid compd.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a fireproofing / refractory composition containing a high concentration of a boric acid compound which can be used as a fireproofing / refractory material with no pollution, while making wood and natural fibers durable. It relates to the fireproof and fireproof materials used.

[0002] If there is an inorganic binder that makes wood and natural fibers that are environmentally friendly and durable and is pollution-free, durability is created, and it becomes a fire and fire resistant material to prevent fires and to recycle the earth. It will be a material expected in the future to return to, and it will create a wide range of applications.

For disaster prevention, there is a demand for a fireproof material which makes daily commodities, clothes, furniture and building materials flame-retardant and does not generate harmful gas or smoke in the event of a fire. Furthermore, in the global environment, it is an era where natural products such as wood, fiber, and paper products must be protected from insects and antiseptic to be durable and save resources.

Since the product of the present invention can achieve these objects, it can be widely used in various industries. Further, it can be used as a pollution-free flame retardant for synthetic resins that are mass-produced.

[0005]

2. Description of the Related Art Conventionally, natural fibers such as wood, cotton, and hemp have been replaced with synthetic resin products which are petroleum products because they are not durable. However, synthetic resin products produce pollution by generating harmful gas and black smoke at the time of fire, so in order to prevent them, they are mixed with flame retardants and commercialized. This flame retardant includes halogen compounds, phosphorus-containing compounds, nitrogen compounds, metal compounds and the like, and it has been reported that there is concern about the gas generated during combustion.

[0006]

Conventionally, boric acid compounds have been used as flame retardants, but these have only been dilute solutions. Using dilute solutions does not give fire protection.

In order to obtain fire protection and fire resistance, emulsion must be added because it must not be precipitated and powdered at room temperature and at the time of combustion, and it will not be effective unless it is made into a coating film. However, this is flameproof but not fireproof.
In addition, in order to inject fire into wood to generate fire resistance, solid matter must be left to the extent that it is dried to cover the tissue surface.

Phosphoric acid or guanidine sulfate is generally used as a flame retardant. However, in order to use a large amount of this as a fireproof material, there are many problems in terms of its injection and generated gas. is there.

Although the semi-incombustible wood has been commercialized in the market, the manufacturing process is not simple and the cost is high. For bonding materials such as chipboard, MDF, rock wool board,
Although urea resin, melamine resin, phenol resin, etc. are used, the synthetic resin content concentration in commercial commercial products is 40 to 65%, and although the concentration is actually reduced, it is around 40%. It is the content concentration. A fireproof / fireproof binder cannot be substituted without the above concentration.

To date, with an inorganic solution that is non-polluting when burned,
There was no high-concentration coating material. The material that can be injected or impregnated into wood or natural fibers must be a solution that can be injected into the microstructure. A suspension with particles produces no effect.

It is known that boric acid compounds have antibacterial / insect / mildew-proofing and flameproofing effects, but since they do not form high concentrations and do not form a coating film, they are not suitable for fireproofing / fireproofing materials. did not become. Although the conventional preservatives are effective in preserving, they have not been fireproofing materials.

[0012] Commercially available flame retardants have the effect of kneading into a synthetic resin and generating a decomposed gas in the event of a fire to extinguish a fire, and are generally used. It was difficult to maintain the fire protection effect for more than a minute. In addition, many of these decomposed gases contained nitrogen gas and chlor, which are not preferable for disaster prevention. Liquid organic or resin products used as commercially available raw materials have a solid content concentration of 65%. Converted to solubility 65/35 =
Since the known solubility of boric acid compound corresponding to 1.857 is about 5%, the solubility seems to be impossible 1.
It was necessary to make 50-200% of a stable solution without precipitation.

For the mixing with the synthetic resin, fine powder may be kneaded, or the resin surface may be coated and kneaded. In any case, a high-concentration product should be used in order to obtain a dried product having an action and effect. Needed.

Although there is a demand for a non-combustible inorganic fiber composite product, an inorganic prepreg product has not been realized. Similarly, the advent of flame-retarded sheet-like or molding compounds is desired.

Binders of wood and natural fibers must be neutral and acidic. Inorganic fireproof agents that are inexpensive are boric acid-containing compounds and phosphoric acid compounds, but none of them alone form a film. Borax and boric acid have low solubilities and do not have high concentrations. Phosphoric acid is a strong acid although it has a high concentration.

That is, there has been no method for adjusting the pH to a desired value in addition to a high-concentration solution of a boric acid-containing compound. Further, the boric acid-containing compound solution did not become a solution due to precipitation due to a change in temperature, and it did not become a fire / fireproofing material because it powdered when dried and did not form a coating film.

A boric acid compound is a water-soluble substance which does not use a solvent, does not generate a harmful decomposition gas in the case of a fire, has antiseptic and insect-proof properties, and is inexpensive in price. However, the known solubility of the boric acid compound (dissolved g / 100 water, 20
(° C.) had a weakness of only about 5% and did not become a high-concentration product.

[0018]

As described herein, the present inventors have added one or more sequestering agents and / or wet-permeable surfactants and a phosphoric acid compound or silanol salt to heat the mixture. However, it is proposed to form a high-concentration boric acid compound composition.

It has been found that the crystal form of the boric acid compound changes during the process of adding the mixture. That is, it was found that when the reaction solution was heated to a high temperature, it became an apparently transparent solution, but when observed under a microscope, the crystal form remained, which caused precipitation when the temperature returned to room temperature.

Therefore, the inventors of the present invention have clarified means and methods for forming a stable high-concentration boric acid compound aqueous solution without precipitation or precipitation, and for forming an amorphous coating film during drying.

[0021] There is no heat resistance improver for improving the heat resistance temperature of polyolefin-based, polyether, polyester-based or a mixture thereof synthetic resin, and it is commercialized by blending a low heat-resistant material with a high heat-resistant material. Therefore, various grade products exist with a difference in heat resistance of 10 to 20 ° C.

Although various flame retardants are regulated or planned to be regulated in the future, no pollution-free flame retardants have been found to replace them. Although there are insect repellents, rodents, and fungicides which generate decomposed gas at room temperature or when heated, a product that is storable and does not generate harmful gas is desired because it may cause environmental pollution due to the generated gas. Although boric acid compounds are known to have insecticidal, mildew-proofing, and rodent-proofing and other actions, a high-concentration solution was required for general use.

In order to make the boric acid compound into a high-concentration solution,
The crystals of borax and boric acid must be made into a nanomicron size and made into a colloid or made amorphous. It has been found that even if a boric acid compound is complexed with a sequestering agent and micelles are attempted to be micelles with a surfactant, those crystal forms remain in the solution, causing problems such as precipitation and precipitation.

Further, even if the acid was added, the crystal of the boric acid compound did not become fine, but in some cases, it became coarse. Even if heating conditions were added to these, it was difficult to keep the high concentration solution at room temperature. Physically, the colloidal mill was attempted to be finely combined with the above method or alone, but it was difficult to form a stable fine colloid liquefaction and to make it amorphous. This state is shown in FIGS.
9 is a micrograph of the crystal structure of No. 9.

On the other hand, in practice, in order to use the boric acid compound as a fireproof / fireproof material, the composition containing the boric acid compound is 1
It should have a solubility of 0 to 300% and the dry film should be flat or coated.

The inventors of the present invention delay the heat conduction of the method of making various substances flame-retardant by shielding them with a heat-resistant coating film without decomposing them, as compared with the conventional method of deoxidizing with a pyrolysis gas. We thought that it would be better to solve it by the heat absorbing effect.

The present inventors have proposed a boric acid compound-containing composition,
The present invention proposes that wood and natural fibers can be made semi-inflammable and flame-retardant. In this case, if the solution is a high-concentration solution, the injection amount is small, the drying is fast, and the productivity is high.

The above-mentioned means for making the synthetic resin flame-retardant requires adhering the solid content of the solution of the present invention to the surface of the synthetic resin or pulverizing the solution and kneading it into the synthetic resin. Since it has to be dried and the amount of adhesion must be increased, it is necessary to increase the concentration of the boric acid compound-containing structure. In addition, since the boric acid compound-containing composition is a fireproof / fireproof material, it is a heat resistant coating and must not decompose at high temperatures. Furthermore, the endothermic effect is required.

That is, the crystalline boric acid compound must be a 100 to 300% solubility solution which cannot be conventionally established, and the crystalline must be made amorphous to form a fire resistant coating film.

The present invention has solved these problems.

[0031]

SUMMARY OF THE INVENTION A first invention proposed by the present inventors is that a boric acid compound is added to an aqueous solution of a sequestering agent or an aqueous solution of a wet permeable surfactant at room temperature in an amount of 5 g / water.
A high-concentration boric acid compound obtained by mixing so as to have a solubility equal to or higher than 0 g, and hydrothermally reacting the mixture at 60 ° C. or higher. In the second invention, the boric acid compound is added to an aqueous solution of a sequestering agent or an aqueous solution of a wet permeable surfactant at room temperature at 5 g / water.
It is obtained by mixing so as to have a solubility equal to or more than 00 g, hydrothermally reacting this mixture at 60 ° C. or more, and further adding either one or both of phosphoric acid or a silanol salt having a siloxane skeleton. It is a high-concentration boric acid compound. A third aspect of the present invention is that a boric acid compound is mixed with an aqueous solution of a sequestering agent or an aqueous solution of a wet penetrating agent so as to have a solubility equal to or higher than 5 g / 100 g of water at room temperature. A high-concentration boric acid compound obtained by adding an acidic or weakly alkaline mineral acid salt and hydrothermally reacting this mixture at 60 ° C. or higher. And a fourth invention is that a boric acid compound is mixed with either an aqueous solution of a sequestering agent or an aqueous solution of a wet penetrating agent so that the solubility of the boric acid compound at room temperature becomes 5 g / 100 g of water or more. A weakly acidic or weakly alkaline mineral acid salt is added to the mixture, the mixture is hydrothermally reacted at a temperature of 60 ° C. or higher, and either one or both of phosphoric acid and a silanol salt having a siloxane skeleton is added to obtain a mixture. It is a high-concentration boric acid compound.

As a fifth invention, the inventors propose a fireproofing / fireproofing composition containing the high-concentration boric acid compound according to any one of the first to fourth inventions.

In the above description, "normal temperature" means 20 ° C. That is, the solubility of the boric acid compound “corresponding to 5 g / 100 g of water at room temperature” means that the solubility exceeds the conventionally known solubility corresponding to 4.7 g / 100 g of water at 20 ° C. There is.

In the above description, "the hydrothermal reaction is performed at 60 ° C. or higher" is to increase the solubility of the boric acid compound. The temperature is set to “60 ° C. or higher” because it is known that at 60 ° C. or higher, borax becomes an insoluble pentahydrate and precipitates. The purpose is to provide a high-concentration boric acid compound in which a boric acid compound does not precipitate. The temperature for the hydrothermal reaction is preferably 60 ° C to 100 ° C.

The pH of the high-concentration boric acid compound can be arbitrarily adjusted to 4 to 8 by adding one or both of the phosphoric acid and the silanol salt having a siloxane skeleton.

Furthermore, the present inventors have used the following fireproof / fireproof materials and binders using the fireproof / fireproof composition containing the high-concentration boric acid compound according to the first to fourth inventions. suggest.

1. The fireproofing / fireproofing composition containing any one of the above high-concentration boric acid compounds is obtained by impregnating wood by combining normal pressure injection, pressure injection or reduced pressure injection methods, and drying this. A fireproof and fireproof material.

2. A composite of a fireproofing / fireproofing composition containing any one of the above high-concentration boric acid compounds, with either a synthetic resin or a latex, and a composition containing either an isocyanate group or zinc oxide or an isocyanate group or zinc oxide. Fireproof / fireproof material obtained by mixing and coating or impregnating on any of textile products, wood chips, wood fiber products, paper products or inorganic sheet products, and drying at room temperature or by heating.

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

4. A fireproof / fireproof material obtained by applying, dipping or injecting a fireproof / fireproof composition containing any of the above high-concentration boric acid compounds to a textile product, a paper product, or a wooden product, and then drying. .

5. It is characterized in that the fireproofing / refractory composition containing any one of the high-concentration boric acid compounds is applied to the surface of a synthetic resin solid, a silicone resin or a fluororesin or kneaded, and dried to have high heat resistance. Fireproof / fireproof material.

6. A fireproof / fireproof composition containing any of the above high-concentration boric acid compounds is impregnated into an inorganic or organic woven or non-woven fabric, which is a semi-dried prepreg sheet or a dried sheet mold compound. Material.

7. A fireproof / refractory composition containing any of the above high-concentration boric acid compounds and either carboxymethyl cellulose or carboxymethyl hydroxyethyl cellulose were mixed, and an inorganic or organic woven fabric or non-woven fabric was impregnated, and this was semi-dried. Fireproof and fireproof material made of prepreg sheet or dried sheet mold compound.

The present invention provides a method of increasing the concentration of borax or boric acid (hereinafter referred to as "boric acid compound") to a known level or higher and preventing precipitation at low temperature by using a sequestering agent (hereinafter referred to as "chelating agent"). Alternatively, a wetting and penetrating surfactant (hereinafter simply referred to as "surfactant") was used. As a method of arbitrarily adjusting the pH of the solution, at least one of alkaline borax, boric acid, phosphoric acid, condensed phosphoric acid, a salt of phosphoric acid or a salt of condensed phosphoric acid is used in common. Even if the boric acid compound is made into a solution by using the chelating agent or the surfactant to form an ionic micelle, it is powdered when dried. The present inventors were able to form a dry coating film without powdering by mixing a silanol salt having a siloxane skeleton. Alkoxides may also be used in place of the silanol salt.

The present inventors have made possible a method of adjusting the solubility of a cement composition to be hydrated or enhancing the solubility above a known solubility by using a chelating agent (for example, Japanese Patent Publication No. 4-4221 and Japanese Patent Publication 48-40444
issue). In addition, the inventors of the present invention have found that 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, and the chelating agent is a general-purpose EDTA. And oxycarboxylic acids such as gluconic acid, citric acid and ketocarboxylic acid, inosinic acid or salts thereof. Further fluoride,
It was clarified that chromium, zinc, boric acid compounds and phosphoric acid compounds also have a mutual reinforcing effect with the chelating agent.
Further, a surfactant having a chelating effect also has an effect of forming a water-soluble metal into an ion micelle to enhance the solubility.

In addition to the above, the chelating agents include NTA and ED
There are various kinds of sugar acids such as TA-OH, DTPA and the like. The surfactant of the present invention includes an anionic surfactant in which the hydrophobic group is carbon only or a chain bond containing an element other than carbon, and a polycyclic anionic surfactant in which a natural raw material is used for the hydrophobic group. Furthermore, the cationic surfactants composed of alkylamine salts and quaternary ammonium salts showed effective effects. In addition, the chelating agent of the present invention is not limited to the above-mentioned items, and an admixture of a boric acid compound, which increases the amount of dissolution to a transparent solution at a known solubility or higher under various temperature conditions,
Each can be mixed and used according to a standard method.

The silanol salt having a siloxane skeleton for coating the dissolved ionic micelles in the present invention is an aqueous film-forming inorganic compound previously invented by the inventors, and is disclosed in JP-A-4-239079. And U.S. Pat. No. 504
No. 9316 and the corresponding Japanese Patent Publication Nos. 7-365 and 7-14801. In addition, Material Technology Vol. EVA of 9, 1991 and the Iron and Steel Institute International Convention
LMAT, 1989.

That is, an inorganic substance hydrated and synthesized from a metal (silicon, aluminum and other metals) and a mineral acid (sulfuric acid, phosphoric acid, boric acid, hydrofluoric acid, nitric acid or their subminus acid) or a mineral acid salt and an alkali metal. A polymer. Silanol salts using ammonia in place of the mineral acid are also within the scope of this invention and are used to shorten afterflame time. Further, the silanol salt is not limited to the above, and for example, alcohol-modified ethylsilanol or alkoxide can be used.

The known solubility of borax decahydrate is only 4.7 g / 100 g of water at 20 ° C., and at 60 ° C., the solubility is not increased and pentahydrate is precipitated. Even with boric acid, 3.
992 g / 100 g water, 40.2 even at 100 ° C
g / 100 g of water (Physical and Chemical Dictionary P1260-126
1, 1976). That is, it was clear from the known solubilities of boric acid and borax that the concentration did not exceed 5% at 20 ° C. Actually, the solid content of the synthetic resin solution of the commercially available binder is
% By weight based on the total amount, for example, 45% means 45 g / 55 g, that is, 81.8% according to the above-mentioned solubility rate.
However, it is practically used at a concentration of about 40%.
When converted into the solubility of the boric acid compound, it becomes 66.6%.

The inventors have found that a practical solid content of 50 g / water 1
The following test was conducted to determine whether a solubility of 00 g (water) was possible.

Borax 10 250 parts hydrous salt, 250 parts boric acid 5 in total
A dissolution test was carried out under the compounding conditions in which 00 parts was added to 1000 parts of water, and the addition amount of various chelating agents and surfactants was 20 parts. After adding the additive to water and heating to 30 ° C. or higher, the borax / boric acid-containing mixture (hereinafter referred to as “boric acid-containing compound”)
And continue heating to obtain normal temperature maximum temperature boiling temperature, 20
The results of observation by cooling to ℃ are as follows.

As typical selections of the additives, citric acid is used for oxycarboxylic acid, ascorbic acid is used for oxyketocarboxylic acid, sodium inosinate is used for nitrogen compound, ethylenediaminetetraacetate (EDTA) is used for sequestering agent, and anionic surfactant is used. , Sodium dodecylbenzene sulphonate (F-25), Sodium alkyl naphthalene sulphonate (NB-L), Sodium dialkyl sulfosuccinate, Alkyl diphenyl ether disulphonate (SSL), Special carboxylic acid type (ASK) , Naphthalene sulfonic acid formalin condensate soda salt (NBL), special aromatic sulfonate formalin condensate soda salt (SS
-L), special polycarboxylic acid type polymer (PS, 52
0), stearylamine acetate (86) and stearyldimethylammonium chloride (D86P) were used as cationic surfactants.

Regardless of which one was used, a transparent solution was obtained under the above-mentioned compounding conditions, which was maintained up to a liquid temperature of 35 ° C., and was gradually deposited. Of the total weight by heating and evaporation, the hydrated residual precipitation showed the highest precipitation amount of about 25% in the above NBL / ASK at 20 ° C., but the remaining amount was within 15% and the ketocarboxylic acid within about 10%. It showed the highest solubility. That is, 33.8
The solubility was not less than 43.1 g / 100 g of water, which was a known solubility or higher.
At 20 ° C., the pH was around 7, and even if the mixing ratio of borax and boric acid was changed, the pH could not be adjusted to the range of 4 to 8 arbitrarily.

A cotton cloth was impregnated with the above solution and dried to give a powder. However, if 10 parts by weight or more of the emulsion was mixed, a coating film was formed and fire resistance was produced.

The inventors of the present invention applied the solution to a slide glass according to the mixing stage of the additives in the above test and observed the dry coating film. As an example of the chelating agent, oxykeltocarboxylic acid, as an example of the surfactant anionic alkylnaphthalene sulfonic acid (NBL) and cationic stearylamine acetate (SAA) when using the change of the crystal form, 500 cc of aqueous solution at 80 ℃
The above was kept and observed. This result is 2
The photograph was taken at a magnification of 5 times, and further magnified 20 times by a video, for a total of 500 times, and shown in the attached photomicrographs of the crystal structures of FIGS. 17 to 19. FIG. 17 shows the case where oxykeltocarboxylic acid is used, FIG. 18 shows the case where alkylnaphthalene sulfonic acid is used, and FIG. 19 shows the case where stearylamine acetate is used.

In each drawing, (a) is borax (hereinafter referred to as "B").
N)) is mixed with (b),
In the state of (a), a chelating agent and a surfactant are further added for each 2
This is the case when g is mixed. (C) is boric acid (hereinafter “BA”)
(D) is mixed with 100 g, and (d) is the case where 20 g of phosphoric acid (89% pure) is further mixed with the state of (c).

As a result of this observation, it was discovered that the crystallinity was made finer to form a net-like bond or a coating film.

Therefore, the present inventors further conducted research to make the crystalline substance of the boric acid compound amorphous and form a stable colloidal solution.

Borax and boric acid may be used individually or in a mixture to form an aqueous solution, which is heated and stirred from room temperature until boiling.
Even if the crystal form was miniaturized, it could not be miniaturized because there was no basic shape change.

In addition to this, EDTA and NTA that have already been proposed
Chelating agents such as, citric acid or diketogluconic acid, oxycarboxylic acids such as inosinic acid having nitrogen or phosphorus, or anions or cations or neutral surfactants, ethylene glycol or polyethers (PPG / PTM
EG / PTG) is mixed with boric acid compound in water, stirred, heated, and passed through a colloidal mill.
Crystals of borax pentahydrate formed above 60 ° C remained.

Furthermore, even if borax soda is added to phosphoric acid, sulfuric acid, or nitric acid to form a soda salt, the crystal form does not become fine, but the crystal becomes coarser depending on the conditions. There was found.

From the above observation, there was a need for a catalyst acting to promote crystal change or a coupling acting. Under the above conditions, an alkali metal salt of a weak acid or a weak alkali, for example, sodium fluoride (PH7.74), sodium phosphite (PH7.02), sodium sulfite (PH9.8).
7), sodium nitrite (PH 9.04) and sodium borofluoride (PH 6.2) were selected and mixed to easily form a solution. As the alkali metal, Na, K and Li can all be used.

The dry coating film was changed to a glassy or film-like substance, and no crystalline form of boric acid compound was found. The salt of the chelating agent or the surfactant is preferably a monovalent salt.

85 to 89% phosphoric acid was added to the above composition in an amount of 1 to 20.
By adding parts by weight, the pH could be adjusted to 4 to 8 and the low temperature precipitation was also improved. The phosphoric acid used for adjusting the pH is not limited to orthophosphoric acid, and includes condensed phosphoric acid and salts thereof, and also has an alkaline chelating effect of borax. When a cotton cloth was dipped in these solutions and dried, the film-forming property was somewhat improved.

It is considered that the dissolution of boric acid and borax with the above-mentioned chelating agent and surface active agent causes ion micelle formation and association. When the silanol salt having the siloxane skeleton was used as the binder, the film forming property was improved.

Said silanol salt (S
When 1 to 30 parts by weight of a 20% solution of i, B, Na) was mixed subsequently with phosphoric acid in the above formulation, the fire-resistant film-forming property was improved. 100 parts by weight of the solution of the present invention (hereinafter referred to as "PHN") in which 5 parts by weight of the silanol salt is mixed with the above formulation.
A glass non-woven paper of g / m ² was dipped and dried.
The fire resistance was tested on the product subjected to such treatment and the untreated product. When a burner having a tip temperature of 900 ° C. was applied to the untreated product, holes were formed in 1 to 2 seconds, but the treated product exhibited fire resistance that required 15 seconds.

The PH of the PHN solution is set to 5.8 and 60
A melamine resin having a concentration of 20% was mixed to obtain a binder. When 100 parts by weight of this binder was mixed with 200 parts of waste newspaper pulp and hot-pressed at 140 ° C., it was thermoset without a curing catalyst.

When the silanol salt was excessively blended and mixed, a tufted fibrous combined ceramic was obtained.

On the other hand, when the silanol salt mineral acid was HNO ₂ (Si, NO, Na), for example, needle-like crystals were formed.

In the above reaction, if the solution was simply a high-concentration solution, a high-concentration solution of the boric acid compound could be prepared without adding phosphoric acid or other mineral acids or the aqueous film-forming inorganic compound solution. One of the objects of the present invention is to make the solution of the present invention into a fireproof / fireproof material. For that, it must remain without decomposition at high temperatures.

By adding the aqueous film-forming inorganic solution previously proposed by the present inventors, it was possible to stabilize the above boric acid compound, the surfactant and the high-concentration boric acid compound solution of a mineral acid salt and to form a refractory material. . The reason for its existence is that DTA-TG and FT in the latter stage
This can be explained by the result of analysis by IR.

Since the raw materials of the solution of the present invention are borax around pH 9 and boric acid around PH 5, the pH of the produced solution can be adjusted by the ratio of use. If Na ₂ B ₄ O _{7 as a} borax component exceeds H ₃ BO ₃ as a boric acid component in a weight ratio, the pH is ₇ or more, and if the boric acid component is large, the pH is 7 or less.

The effects of the present invention could be confirmed by microscopic observation. CAD-600 (manufactured by Kao Corporation), which is a polydicarboxylic acid type surfactant, is added to 20 g / 1000 cc of water as described above, and borax and boric acid are each added to 250
When a total of 500 g of g was added and observed on a glass plate,
Calcite-type and monoclinic columnar crystals were scattered. Aggregate crystals were found in the dried product. Subsequently, when 50 g of phosphoric acid was mixed and stirred, needle-like crystals were gathered in a chestnut-like shape with the boric acid compound as the nucleus. To this, 100 g of a 7% liquid of the silanol salt containing (Si, B, Na) was mixed and stirred. Although the solution was transparent, when it was dried and observed, the crystals before mixing were changed to an amorphous glassy substance, and a coating state in which a nonwoven fabric was bonded in a random network was observed. Depending on other conditions, it changed into thread-like crystals, ginkgo leaves, and tuft-like crystals, and was also in the form of reticulated coating.

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 the phosphoric acid increases the number of strip-like crystals to form a matrix-shaped matrix, and when the silanol salt is added, The appearance of forming a randomly bonded coating film such as a melt-bonded synthetic resin nonwoven fabric was obtained by microscopic observation.

An attempt was made to inject the above-mentioned solution (PHN) of the present invention into cedar wood. Using a wood injection device made by Sato Iron Works, owned by Kitchen House Co., Ltd., injection was performed by combining normal pressure, reduced pressure, and pressure. Since the boric acid compound PHN solution is a transparent solution, it was possible to obtain an injection amount close to the theoretical value of 280% by weight of cedar wood. This was subjected to a JIS fireproof test and a 6-minute heating test. TDθ was 100 and CA was only 6. That is, sufficient results were obtained to pass JIS flame retardancy class 3.

5 mm thick non-woven linen fabric (manufactured by Tokos Co., Ltd.)
Was immersed in a liquid in which the boric acid-containing compound PHN solution used above and 60% melamine (Sanwa Chemical Co., Ltd.) were mixed at a ratio of 80:20, and then heat-cured and molded at 130 ° C. When this product was burned with a simple burner, it only carbonized without producing a flame. In the same manner, the PHN solution was used as a binder to solidify and mold the waste newspaper fiber, and a fireproof test of heating for 20 minutes was performed. As a result, a test result close to JIS Flame Retardant Class 2 was obtained.

Takeda latex 45% liquid 10% and special isocyanate 3% were added to prepare a mixed liquid, which was added to the PHN solution and coated on a cotton cloth. And showed resistance to washing.

A thermosetting resin or sulfur can be used as a crosslinking agent for the PHN / latex mixture of the present invention. Methylated methylolmelamine is particularly effective.

When zinc white was used in place of the above-mentioned isocyanate and was coated on paper and cured at room temperature, rubber elasticity was produced and flame retardancy was obtained. When the paper was a sheet of alumina silica 1 mm, the defect of weak tearing of the sheet was improved and the sheet became incombustible.

The known solubility of the boric acid-containing compound at 20 ° C. is about 5%, but according to the invention it is above 70%.
Solubility of 120 g / 100 cc of water was possible at 50 ° C or higher. The pH of the borax solution is around 9, and the pH of the boric acid solution is around 5.
There is an effect that H5 to 8 can be arbitrarily adjusted.

Further, according to the present invention, since a high-concentration solution of a boric acid-containing compound was made into a transparent liquid, it could be injected into a 1-micron pipe of wood and a dry coating film could be formed. With one injection-drying, the wood produced the effect of being able to be made into the JIS flame-retardant grade 2-3 grade material which kept the natural color and texture. When impregnated with the solution of the present invention, natural products such as paper, cotton and linen products are made flame-retardant, and glass, rock wool and inorganic fiber products are heat-reinforced. Further, since the high-concentration solution of the present invention becomes a binder such as a synthetic resin,
When used as a binder for flame-retardant chipboard, particle board, MDF, and pulp molded products, it became a flame-retardant product that does not generate combustion gas or smoke.

Further, as a result of the following improvements, it was possible to produce a boric acid compound having a high solubility of 100 to 300%, which was impossible in the prior art.

It was found that even if a chelating agent or a surfactant is added to water and stirred, sufficient action and effect will not be produced unless it is dispersed in a uniform colloidal form. Action to disperse the above-mentioned weakly alkaline or acidic sodium fluoride, sodium phosphite, sodium sulfite, sodium nitrite, sodium borofluoride into a chelating agent or a surfactant in a weight less than half that of colloid I discovered that These were glass films formed by first adding the weakly acidic substance or weakly alkaline substance to the chelating agent or the surfactant, then adding borax and further adding boric acid. After adding the chelating agent or the surfactant and the borax, or at the same time, adding the weakly acidic substance or the weakly alkaline substance and further adding boric acid changed the crystals of the boric acid compound into a coating film. By this action, it was possible to realize a high-concentration solution of a boric acid compound having a solubility of 100 to 300%, which was not possible until now.

The aqueous film-forming inorganic compound previously proposed by the present inventors is a silanol salt, but the addition of a small amount (addition of solid content of 5% or more of the boric acid compound) to the boric acid compound of the present invention provides fire resistance. Bonding occurred. Probably based on a coupling-like action.

Cedar material 15 mm × 200 mm × 300 mm was placed in a can filled with the PHN 40% liquid (NF-MH) of the present invention, depressurized, and then pressure-injected at 20 kg / cm ² , and 630
The amount of solid content remaining after drying is 2 at an injection rate of 1 liter / m ^3.
It was confirmed to be 50 kg / m ³ , and a quasi-nonflammability test was carried out using a Toyo Seiki fireproof tester. TDθ37, CA6, Af18
I got a sec record.

Also, carboxymethyl cellulose (CM
When C) or carboxymethyl hydroxyethyl cellulose (CMHEC) was added in an amount of 0.1% or more, a heat-resistant bonding property was produced despite being an organic substance.

[0087] said to hemp fibers of 125g / m ² PHN (N
F-MF) 20% solution was added with 1% CMC and dried. Even if it burned with a burner with a tip of 1000 ° C or turned red due to a fire, it couldn't pass through. A thermosetting resin such as a urea resin, a melamine resin or a phenol resin can be freely mixed and used together with the solution of the present invention.

Therefore, the solution of the present invention is impregnated into glass fiber or carbon fiber (not limited to these) and used as a completely inorganic or in combination with the above-mentioned thermosetting resin to prepare an unreacted prepreg sheet containing water. It was possible to mold by heating, drying, and curing.

The coating film-forming substance of the present invention described above is B--O.
Since it has a reactive group (to be described later FTIR), it has miscibility with a synthetic resin having an ether / ester bond, and has heat resistance and endothermic action. The moldability of the resin obtained by mixing PP (manufactured by Mitsui Petrochemical Co., Ltd.) and the liquid PHN (NF-MF) of the present invention having a solid concentration of 30% in the same weight and drying was not different from that of normal molding (Toyo Test Lab Mill test result). Further, in the flame-retardant HB test, it was shown that the present invention has heat resistance of 5 minutes and 10 seconds, compared to 1 minute and 50 seconds for a normal product. When 50 parts by weight of the solid powder of the PHN product of the present invention was kneaded with PP, the HB test was 6 minutes and 30 seconds.

The olefin system, which has been regarded as difficult in the past, worked effectively. This was put into an extruder to form a sheet, which was laminated with glass cloth and formed into SMC, and a helmet could be hot press formed from the sheet.

An example will be described below.

[0092]

Example 1 The following experiment was tried using borax decahydrate with a purity of 99% or more made in the United States, boric acid and 89% phosphoric acid (manufactured by Taihei Chemical Co., Ltd.). 1000cc of water, EDTA2
5g, 10g, 20g, 30g, 40g, 50g of Na
Was selectively added, mixed and dissolved, and heated to 30 ° C to 60 ° C. A total of 500 g of 250 g of borax and boric acid were mixed. Even if there was an undissolved residue at 30 ° C. with a mixed amount of 5 g of EDTA, it was completely dissolved at 80 ° C. or higher. The undissolved residue decreased at 30 ° C even with other addition amounts,
It was completely dissolved at ℃ or above. However, precipitation started as the liquid temperature decreased to 35 ° C or lower, and the maximum precipitation at 20 ° C was 10% of the total weight. That is, a solubility of 35 g / 100 cc or more was obtained. Re-heat again, 70 ℃ until completely dissolved
It took the above.

[0093]

Example 2 A similar experiment was conducted by substituting the chelating agent of Example 1 for citric acid, ascorbic acid (ketocarboxylic acid) and sodium inosinate, which are oxycarboxylic acids.
Total dissolution at 75 ° C or higher, but 15-25% by weight at 20 ° C
Was deposited. That is, the solubility was 13 to 28 g / 100 cc of water, which was higher than the known solubility.

[0094]

Example 3 A similar experiment was conducted using the following anionic surfactant or cationic surfactant in place of EDTA of Example 1 above.

SS-40N as anionic surfactant
(Fatty acid salt, manufactured by Kao Corporation), Emal 71 (alkyl sulfate), Neoperex 25 (sodium dodecylbenzenesulfonate), Perex NB-L (sodium alkylnaphthalene sulfonate), Perex OT
-P (sodium dialkyl sulfosuccinate), Perex SS-L (sodium alkyl diphenyl ether disulphonate), Latemul WX (sodium polyoxyethylene alkyl ether sulfate), Latemul ASK (special carboxylic acid anion), Demol NL (Β-naphthalene sulfonic acid formalin condensate soda salt), Demol SS-
L (special aromatic sulfonate formalin condensate soda salt), Demol EP Poise 521 (special polycarboxylic acid type polymer anion), ethylene glycol, and polyprepylene glycol were used.

Acetamine 8 as a cationic surfactant
6 (Stearylamine acetate), Coatamine 24P
(Lauryl trimethyl ammonium chloride) and Amphitol 24B (lauryl betaine) were used.

In any case, a mixture of boric acid and borax was added at a temperature of 60 ° C. or higher and 90 ° C. or higher to a known solubility of 50 g / g or more.
A solubility of 100 g of water was obtained.

However, at 20 ° C. or lower, the total weight is 2%.
0-25% precipitation occurred.

[0099]

[Example 4] Special polycarboxylic acid surfactants WH-Z and CA manufactured by Kao Corporation used as cement admixtures
D-600 was used separately, replacing the EDTA of Example 1 above. Although there was an undissolved precipitate of about 10% of the boric acid compound at 50 ° C., 50 g of the 89% phosphoric acid (5% to water, 10% to boric acid compound) was added and dissolved.

[0100]

Example 5 Using the polydicarboxylate CAD-600 used in the above example, 1000 g of borax / 100 of water.
An experiment was attempted showing a solubility of 0 g. CAD-600 is 1
Mix 100 g of 0% / borax in water and heat to 6
Even at 0 ° C, an undissolved residue of borax pentahydrate was produced. When 100 g of 89% phosphoric acid used in the previous example was added and mixed, a transparent solution was obtained. A slight precipitate was observed at 20 ° C. Later precipitation occurred.

[0101]

[Embodiment 6] The "cement admixture consisting of special anhydrite" according to the invention of Japanese Patent No. 1189741 is a dihydrate gypsum mixed with 1 g of calcium fluoride / 100 g of gypsum at 750 ° C.
However, it has the effect of promoting dissolution. In place of 20 g of EDTA of Example 1, the anhydrite 10 was used.
g (CaF ₂ / boric acid compound = 0.02%) and 2 g of citric acid (2 g / 500 g, 0.4%) as a chelating agent were used. When the temperature was raised to 80 ° C., the boric acid compound was completely dissolved.

[0102]

[Example 7] A process in which the solubility of boric acid-containing compound is 70 g / water of 100 g and the pH is arbitrarily adjusted to 5.5 to 9 to give a transparent solution is shown below.

300 g of the special polycarboxylate Mighty-WH-Z manufactured by Kao Corporation was mixed with 10 kg of water. P
H was 8.85. 1.2 kg of borax decahydrate having a purity of 99% made in the United States was mixed with this. PH was 8.9. Even when heated to 50 ° C, there was an undissolved residue.

500 g of 89% phosphoric acid was mixed. PH is
It became 4.98 at 68 ° C. and there was no undissolved residue.

In addition, (S
When 500 g of a 23% silanol salt liquid having a siloxane skeleton having a composition of i, B, Na) was mixed, a transparent liquid was obtained, and the pH was 5.27 at 56 ° C. While continuing to heat it, mix 2 kg of 99% boric acid made in the US
Became 3.12 at 72.8 ° C., and further mixed with 500 g of boric acid, the pH became 3.08. PH of 5.38 was obtained by mixing 3.3 kg of the alkaline borax. It was transparent at 50 ° C or higher.

A solubility solution of 70 g of the boric acid-containing compound / 100 g of water was obtained.

[0107]

[Embodiment 8] A solid content measuring method of heating at 105 ° C. for 3 hours,
# 130 with solid content of 20% or more and solid content of 30%
The above-described # 140 was adjusted with the following composition while heating within 80 ° C.

# 130 # 140 Water 100 Kg 100 Kg WH-z 1.2 CAD 6 Borax 22 Borax 35 Boric Acid 18 Boric Acid 35 Phosphoric Acid 5.4 Phosphoric Acid 7.5 MH 5 MH 2.5 151.6Kg 186 Kg Boric Acid-Containing Compound 40/100 70/100 ratio 105 ° × 3H> 20% solid content> 30% solid content PH 6.5 6.2 In the above formulation example, PH can be easily adjusted to 4 by increasing phosphoric acid. did it. To raise PH, borax /
It is sufficient to increase the ratio of boric acid to borax, and the pH can be adjusted to 7 or 9. Phosphoric acid was not limited to orthophosphoric acid, and almost the same pH adjustment result was obtained even when condensed phosphoric acid was used. That is, by changing the compounding ratio of borax, boric acid, phosphoric acid,
Could be freely set and implemented.

The transparent liquid (# 130 and # 1
40), the crystal structure was observed with a microscope at a magnification of 25 times and further on a video at a magnification of 20 times and a total of 500 times (FIGS. 20 (a), (b), (c),
(D)). (A) is a state where # 130 is made into an amorphous coating film, (b) is a state where # 130 is injected into wood and is coated on the tissue surface, (c) is a state where # 140 is amorphous FIG. 3D is a diagram showing a state in which the coating film is formed, and FIG.

A wood injection experiment was attempted using the above clear liquid. * Equipment used: Sato Iron Works 0.6m diameter x 4m * Wood Kanayama cedar sapwood Specific gravity 0.358 Moisture content 11.5% * Condition a Decompression-750mmHg 30 minutes b Decompression retention time 120 minutes Ha Normal pressure retention time- 50mmHg 60 minutes D Pressing 30K / cm ² 480 minutes e Pressurizing and holding time 5 minutes Heckett temperature 50 ° C * Result 1) Injection amount 874Kg / m ³ (average value) 2) Weight impregnation rate 244% 3) Volume impregnation rate 244% 4) Void impregnation rate 93% This was dried at 60 ° C. for 48 hours. There was no deformation.

The test piece had a natural texture, no discoloration, and was beautiful.

The test results of the surface test of this test body determined by the Ministry of Construction Notification No. 3415 at the Industrial Technology Center are shown below.

[0113] TDshita CA afterflame tertiary secondary tertiary secondary reference <250 <100 <120 <60 <30 seconds # 130 105 8 28 # 140 100 5 25

[0114]

Example 9 The solid content of # 130 in the previous example was 105 ° C.
It was 21.2% when measured for 3 hours. When 80 parts of this was mixed with 20 parts of 60% melamine (Sanwa Chemical Co., Ltd.), the solid content was about 30% each. A hemp 7 mm non-woven fabric (manufactured by Tosco Co., Ltd.) was dipped in the mixed solution to dehydrate the excess, and then thermoset at 130 ° C.

Since the surfactant used had a carboxyl group, it cured in 10 minutes without a catalyst.

In the same fireproofing material test as in the previous example, a test result that passed JIS Flame Retardant Class 3 was obtained.

Even when the above solution was diluted twice with water, and similarly immersed and dried, a test result that passed the JIS flame retardant class 3 test was obtained.

[0118]

Example 10 1 kg of newspaper waste paper pulp (manufactured by Jujo Paper Co., Ltd.) was immersed in the PHN / melamine mixed solution of the previous Example 9 and the excess solution was centrifugally deliquored to make pulp: mixed solution = 1: 2. This one
It was heated at 50 ° C. for 10 minutes and thermoset molding was performed. As a result of a prescribed alcohol combustion test by the Japan Railway Vehicle Machinery Technical Association, 15
Although the thickness was mm, there was no ignition, flame, afterflame, or dust, and the carbonization length was 85 mm, which was 100 mm or less, and the test results equivalent to noncombustible materials were obtained.

[0119]

[Embodiment 11] A 10 mm thick hemp nonwoven fabric (manufactured by Tosco Corporation) was dipped in a solution obtained by diluting the PHN / melamine mixed solution of Example 9 with water twice, and squeezed to obtain a hemp: mixed solution = It was 100: (350-400). This is 130
It was dried and cured at ℃. Although it was white and flexible, it was carbonized even if it was covered with a welding spark, but there was no flame or penetration.

[0120]

[Example 12] Acrylic, styrene and rubber latex (manufactured by Takeda) was added to the urea resin liquid instead of the melamine of Example 9, 10% of the mixed liquid was added, and zinc was further added. 1% of flower was mixed to prepare three kinds of liquids. 100 g / m ² of cotton cloth was immersed in this. After drying, it was treated with Takeda isocyanate. We obtained washing resistance and flame retardancy without flames even when ignited by a burner.

[0121]

Example 13 500 g of water was mixed with 10 g of 40% EDTA solution and heated to 80 ° C. When this was taken as a 25 times photograph with a microscope and further observed with a video of 20 times and a total of 500 times, uniform dispersion was not obtained (FIG. 21).
(A)).

To this, sodium fluoride (manufactured by Hashimoto Kasei Co., Ltd., hereinafter referred to as "N
3 g (referred to as “F”) was added and stirred to uniformly disperse (FIG. 21 (b)).

When 230 g of borax decahydrate (99% purity manufactured by USA) was added thereto and stirred while continuing heating, the crystals were randomly flattened (FIG. 21 (c)).

Further, boric acid (USA 99% purity) 135
When g was added and stirring was continued, the dried coating film formed into a glass and no crystals were found (Fig. 21).
(D)).

To this was added 30 g of a 7% solution of a silanol fluoride salt (made by Comix Co., Ltd., hereinafter referred to as “MF”) prepared from metallic silicon, sodium fluoride and caustic soda, and the temperature was adjusted to room temperature (20 ° C.). No precipitation or precipitation was observed (Fig. 21 (e)). In this 20 ° C state, P
H was 7.2.

By using NBL instead of EDTA,
The same observations as above were made. At the same stage as above,
Similarly, micrographs were taken and observed. Figure 2
2 (a), (b), (c), (d) and (e).

[0127]

Example 14 The solution of Example 13 was treated with water at 150 ° C.
1 to 4 show the analysis results (hereinafter referred to as “NF-MF”) at 20 ° C., 400 ° C. and 800 ° C. by DTA-TG and FTIR.

With DTA-TG, there was little change in weight even at temperatures of 800 ° C. or higher, indicating that the endotherm continued, FT
IR shows that water molecules near 3450 cm ⁻¹ do not disappear even when heated to 800 ° C. and the B—O vibration near 1400 cm ⁻¹ changes by heating, but silanol groups near 1065 cm ^−1. Remained undisappeared even at high temperatures.

That is, the presence of the above-mentioned silanol fluoride salt (aqueous film-forming inorganic compound) was required for fire resistance and fire prevention.

[0130]

[Embodiment 15] Sodium phosphite (hereinafter referred to as "NP") and sodium nitrite (hereinafter "NO") are used as the sodium fluoride in Example 13.
Sodium sulfite (hereinafter referred to as “NS”), and corresponding to the above-mentioned silanol salt (MF) as a substitute for mineral acid, phosphoric acid (Si, P, Na) (hereinafter referred to as “MP”), nitric acid DTA-TG and FTIR when (Si, NO, Na) (hereinafter referred to as “MO”) and sulfuric acid (Si, S, Na) (hereinafter referred to as “MS”) were used were observed in the same manner as in Example 14. The results are shown in FIGS.

In all cases, no decomposition occurred even at 800 ° C. or higher, weight reduction was small, and peaks of hydroxyl groups and silanol groups remained strongly. In terms of chemical composition, this composition can be regarded as having the same effect as adding sodium borofluoride.

[0132]

Example 16 In the previous example, 15 g of borax and 1 boric acid
At 0 g, the surface active agent and chelating agent are 0.3 g, which is 1% or more of the boric acid compound, and the mineral acid salt is 0.2%, which is 1% or more.
With 5 g, a clear solution of boric acid compound having a known solubility of 5 g / 100 g water or more, even if the silanol salt was lacking, was obtained.

[0133]

Example 17 In 500 cc of water, 250 g of borax and 25 boric acid
0 g, 20 g of sodium dodecylbenzene sulfonate and 5 g of sodium phosphite were blended and heated to 80 ° C. or higher by the above method to obtain a transparent liquid. The solubility was 100%. Further, the dryer was set to 120 ° C. and dried for 3 hours to make the water content 5%. This could be pulverized to 200 mesh or less with a ball mill. Solubility of boric acid compound = 500/25
A powder with 0 + 250 = 100% could be easily manufactured.

[0134]

Example 18 Solubility of boric acid compound 200% (200
(g / 100 cc water) shows the experimental results.

To 500 g of water, 45 g of polyethylene glycol maleate as a surfactant was mixed and stirred, and the mixture was stirred at 85 ° C.
Heat to, add 600 g of borax, and add 25 g of sodium fluoride
The heating was continued while adding. To this, 400 g of boric acid was added, and high speed mixing was performed. When it reached 80 ° C or higher, it became a transparent solution. A high concentration boric acid compound solution (1,000 g / 50) with a pH of 6.93 and a specific gravity of 1.37 without adding mineral acids.
It became 0 g water) and maintained a transparent state at 20 ° C. without causing precipitation. However, after several days, a solidified body was formed on the inner wall of the plastic container. On the other hand, 100 g of a 15% MH type silanol salt solution of (Si, BH ₃ , K) was mixed with the above-mentioned solution which was dissolved and clarified at 80 ° C. under high speed stirring.
This solution was a transparent solution even after long-term storage (30 days).

[0136]

Example 19 In the previous Example 18, the surfactant was a typical chelating agent, NTA, Na ascorbate, and anionic sodium dodecylbenzene sulfonate (F) as the surfactant.
-25), sodium alkylnaphthalene sulfonic acid, cationic stearyl dimethyl ammonium chloride, neutral propylene glycol and ethylene glycol were mixed and used, but there was no problem.

[0137]

Example 20 A 125 g roll of hemp fiber (manufactured by Tosco Co., Ltd.) was added to a NO-MO solution having a boric acid compound solid content of 20% with 1% of carboxymethyl cellulose (CMC) (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and a roll coater. It was put in a tank (manufactured by Nippon Dyeing Co., Ltd.), dipped at a speed of 10 m / min, squeezed with a roll and dried at 120 ° C.

The test results of the flammability test method A-2 (Meckel burner method) of the textile products (test results at the Kanagawa Prefectural Technical Testing Center) were: carbonization area 16 cm ^2, afterflame 0, carbonization length 5.5 cm, and afterburn 0. It was Equivalent to non-combustible material.

The results of zero afterflame and afterglow were also obtained for the Japanese paper wallpaper.

[0140]

Example 21 The following combinations (indicated by abbreviations) were tested in Example 13.

Sodium fluoride (NF), sodium phosphite (N
P), sodium sulfite (NS), sodium nitrite (NO) silanol salt (aqueous film-forming inorganic compound), when the above substances are used, sodium fluoride (MF), silanol borate (MH) , Sodium phosphite (MP), sodium sulfite (MS), and sodium nitrite (MO) were used, and the solution of the present invention was produced as a trial with the formulation of Example 13.

NF-MF, NP-MP, NS-MS, N
O-MO, NF-MH, NP-MH, NO-MP, NS
It was freely combined with -MH and the like, but in any case, it became a transparent solution at 20 ° C and no precipitation occurred.
The solution was placed on a slide glass, dried and observed. In all cases, the crystal form of the boric acid compound disappeared, and it was in the form of a flat plate or a coating film.

[0143]

[Embodiment 22] Water 500 cc, sodium polyacrylate 20
g, borax 600 g, sodium fluoride 5 g, boric acid 400 g, silanol borate (MH) 100 cc
A solution having a specific gravity of 6.9, a specific gravity of 1.45, and a boric acid compound solubility of 200% was obtained.

This solution was kept at 80 ° C., and ABS, polyester, PP and PE were immersed therein. It was dried and treated to deposit about 40% solids.

In the flame retardant test (HB), PP and PE were flame-retarded in 7 minutes or more compared with the untreated material in 2 minutes.

For the ABS and polyester, the result of V-0 was obtained in the UL flame retardant test.

[0147]

Example 23 An example in which the solubility of the boric acid compound is 300% is shown below.

Sodium polyacrylate 30 to 500 cc of water
g and 20 g of sodium phosphite were added, and the mixture was heated to 90 ° C.
While continuing heating (while maintaining 90 ° C), borax 100
0 g was mixed slowly with stirring. Next, 50 g of 89% phosphoric acid was added. When this was mixed at high speed, it became almost transparent. Next, 500 g of boric acid was added and stirred at high speed. It became transparent when heating was continued (when 90 ° C was maintained). To this, 100 g of MP (silanol salt (Si, P, Na) having mineral acid as phosphoric acid) was added, and 9
Warming and stirring at 0 ° C. were continued for 5 minutes, and then ended. When the solution temperature was lowered to 20 ° C., the solution was observed and found to be transparent.

[0149]

Example 24 Sodium polyacrylate having a function of a chelating agent as a surfactant (PS52 manufactured by Kao Corporation)
Use 1). The polyacrylic acid soda (PS52
1) Add 5 g to 500 cc of water and add 230 g of borax and 14 parts of boric acid.
0 g was mixed, 3 g of sodium fluoride was added and the mixture was heated to 80 ° C., and then a silanol salt (MF) 7% solution was added to 30 g.
g was added. When this liquid was placed on a slide glass and observed, a smooth coating film was formed and no crystal form was found.

Similarly to the above, sodium polyacrylate (P
S521) is used. Sodium polyacrylate (PS5
21) 5 g was added to 500 cc of water, 230 g of borax was mixed with this, and then 20 g of condensed phosphoric acid (85% reagent) was added to neutralize the mixture, and then 3 g of sodium fluoride, 140 g of boric acid and 7 parts of silanol salt (MF) were added. % Solution (30 g) was added and heating was continued. Heating was completed at 90 ° C., and this liquid was placed on a slide glass and observed. As with the above, a smooth coating film was formed and no crystal form was found.

[0151]

Example 25 A solution of the NF-MF type product of the present invention described in Example 13, which has a solubility of a boric acid compound of 150.
% Carboxymethyl cellulose (CMC) 1
5 g was added and uniformly mixed and stirred. A glass cloth with a basis weight of 200 g / m ² made by Nippon Sheet Glass was dipped into this mixed solution, placed on a polyethylene film and semi-dried. It was further covered with a polyethylene film and left for 7 days. Then, when it was dried and cured at 120 ° C. for 30 minutes, 60 g of solid content adhered.

Even when the tip flame was applied to the burner at 1000 ° C., the cured product was melted and did not penetrate.

A solution of the NF-MF type product of the present invention having a solubility of a boric acid compound of 150% was mixed with 25% by weight of a melamine urea resin to obtain a mixed solution. A glass cloth was treated with this mixed solution in the same manner as above, left for 7 days, and then heated at 150 ° C. for 10 minutes to obtain a thermosetting body.

Using the solution of the present invention, the solubility of the boric acid compound was changed from 20% to 150% to obtain non-combustible materials that passed various hard and soft materials (JIS standard, TDθ 0 after heating for 20 minutes).

[0155]

Example 26 A solution of the NF-MF type product of the present invention described in Example 13, which has a solubility of a boric acid compound of 30%.
Was dried at 150 ° C. for 6 hours to be solidified, and pulverized into powder of about 50 μm. 200 parts by weight of this powder and 100 parts by weight of the plastic material were mixed to obtain a mixture. 100 parts by weight of this mixture and polyvinyl chloride (PV
C) 300 parts by weight, 6 parts by weight of tin stabilizer, and 200 parts by weight of glass chop are mixed, and SM is rolled to a thickness of 3 mm.
It was made into a C sheet. A UL flame-retardant test was performed on the SMC sheet, and it was confirmed that the SMC sheet was a V-0 grade product having self-extinguishing properties. It was also 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.

[0157]

Example 27 A solution of the NF-MF type product of the present invention described in Example 13, which has a solubility of a boric acid compound of 100.
% Was dried at 105 ° C. for 3 hours. When the dried product thus obtained was measured, it could be confirmed that it had a solid content of about 36%.

The dried product having a solid content of 36% and the polycarbonate were mixed in equal weights and dried to obtain a resin to which the product of the present invention was adhered. Similarly, ABS, saturated polyester, polystyrene and the above-mentioned dry product having a solid content of 36% were mixed in equal weights and dried to obtain a resin to which the product of the present invention was attached.

The four kinds of resins thus obtained were processed and tested in a test lab mill of Toyo Seiki.
There was nothing unusual.

Using these four types of resins as test pieces,
When a flame-retardant test (UL-V) was performed, it was confirmed to be a V-O grade product. Moreover, the generation of decomposition gas and smoke due to heating could be minimized without using any conventional flame retardant material.

[0161]

Example 28 Various high concentration boric acid compound solutions of the present invention described in the above examples were dried to obtain a product having a solid content of 10% or more. This product gelled when mixed with Poval and latex. It was confirmed that the remaining product obtained by squeezing excess water from the gelled product was a flame-retardant product having self-extinguishing property.

When zinc oxide was added in an amount of 1 to 10% to the gelled product, rubber elasticity was produced.

[0163]

Example 29 The following is an example of a solution of the product of the present invention that does not freeze even in winter.

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

The solutions of the products of the present invention were prepared by the following 4 examples. The composition was weight g, and each composition example was prepared in the composition order shown on the left side.

Formulation Sequence Formulation Example 1 Formulation Example 2 Formulation Example 3 Formulation Example 4 Water 500 500 500 500 500 EDTA 4 4 PEG20000 6 5 PPG1900 7 7 NF 10 10 NP 2 5 BN 230 230 230 230 230 P 20 20 20 20 20 BA 140 140 140 140 MF 30 30 30 MP 40 In each case, the hydrothermal reaction was carried out at a temperature of 80 ° C.

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

[0168]

EFFECTS OF THE INVENTION According to the present invention, at room temperature (20 ° C.), there is no precipitation or precipitation, and the stable solubility is 100.
It is possible to provide a high-concentration boric acid compound that can be a high-concentration aqueous solution of 300% to 300% and that can form an amorphous coating film when dried. Further, according to the present invention, the pH of the aqueous solution of the high-concentration boric acid compound can be arbitrarily adjusted within the range of 4 to 8.

Further, according to the present invention, by using the fireproof / refractory material containing a high concentration boric acid compound, the natural resources such as wood and natural fiber can be effectively utilized, and the fireproof / fireproof material is pollution-free and environmentally friendly. Material can be provided.

[Brief description of drawings]

FIG. 1 Sodium Fluoride (NF) -Silanol Fluoride Salt (M
It is a figure showing the differential thermal analysis (DTA-TG) result about the product of this invention by the combination of F).

FIG. 2 shows the room temperature (20
It is a figure showing FTIR in (° C).

FIG. 3 is a diagram showing FTIR at 400 ° C. for the product of the present invention analyzed in FIG. 1.

FIG. 4 is a diagram showing FTIR at 800 ° C. for the product of the present invention analyzed in FIG. 1.

FIG. 5: Differential thermal analysis (DTA-T) for the product of the present invention by a combination of sodium phosphite (NP) and the silanol salt mineral acid with sodium phosphite (MP).
G) It is a figure showing a result.

FIG. 6 shows the room temperature (20
It is a figure showing FTIR in (° C).

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

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

FIG. 9: Differential thermal analysis (DTA-T) for a product of the present invention by a combination of sodium nitrite (NO) and the silanol salt mineral acid using sodium nitrite (MO).
G) It is a figure showing a result.

FIG. 10 shows the room temperature (2
It is a figure showing FTIR in 0 degreeC.

FIG. 11: 400 ° C. for the product of the present invention analyzed in FIG.
It is a figure showing FTIR in.

FIG. 12 is 800 ° C. for the product of the present invention analyzed in FIG.
It is a figure showing FTIR in.

FIG. 13: Differential thermal analysis (DTA-T) for a product of the present invention by a combination of sodium sulfite (NS) and a silanol salt mineral acid using sodium sulfite (MS).
G) It is a figure showing a result.

FIG. 14 is a diagram showing FTIR at room temperature (20 ° C.) for the product of the present invention analyzed in FIG.

FIG. 15: 400 for the product of the present invention analyzed in FIG.
It is a figure showing FTIR in ° C.

FIG. 16 shows 800 of the product of the present invention analyzed in FIG.
It is a figure showing FTIR in ° C.

FIG. 17 is a micrograph of a crystal structure at a mixing stage of a boric acid compound and a chelating agent (oxykeltocarboxylic acid), wherein (a) shows a case where 200 g of BN is mixed,
(B) is a case where a surfactant or the like is further mixed with (a), (c) is a case where 100 g of BA is mixed, (d)
[Fig. 3] is a micrograph of a crystal structure in the case where phosphoric acid is further mixed in (c).

FIG. 18 is a micrograph of a crystal structure at a mixing stage of a boric acid compound and a surfactant (alkylnaphthalene sulfonic acid), where (a) shows a case where 200 g of BN is mixed, (b) shows (a). In the case of further mixing a surfactant and the like, (c) is (d) when 100 g of BA is mixed.
[Fig. 3] is a micrograph of a crystal structure in the case where phosphoric acid is further mixed in (c).

FIG. 19 is a micrograph of a crystal structure at a mixing stage of a boric acid compound and a surfactant (stearylamine acetate), wherein (a) shows a case where 200 g of BN is mixed,
(B) is a case where a surfactant or the like is further mixed with (a), (c) is a case where 100 g of BA is mixed, (d)
[Fig. 3] is a micrograph of a crystal structure in the case where phosphoric acid is further mixed in (c).

FIG. 20 is a product of the present invention having a solid content of 20% or more (# 13
0), the solid content of the present invention product is 30% or more (# 14
0) is a micrograph of the crystal structure of (0), (a) is # 1
30 is an amorphous coating film, (b) is # 130
Is injected into wood, and its tissue surface is coated,
(C) is a state where # 140 is made into an amorphous coating film,
(D) is a micrograph of a crystal structure in which # 140 is injected into wood and the surface of the tissue is coated.

FIG. 21 is a photomicrograph of the crystal structure of the NF-MF type product of the present invention at the production stage, in which (a) is EDT.
A mixed with water, (b) mixed with (a) NF, (c) mixed with (b) borax,
(D) is a state in which boric acid is mixed with (c), and (e) is
It is a microscope picture of the crystal structure in the state where MF was further mixed in (d).

FIG. 22 is a photomicrograph of the crystal structure of the NF-MF type product of the present invention at the production stage, in which (a) shows NBL.
Is mixed with water, (b) is a mixture of NF with (a), (c) is a mixture of borax with (b),
(D) is a state in which boric acid is mixed with (c), and (e) is
It is a microscope picture of the crystal structure in the state where MF was further mixed in (d).

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C09D 101/26 PCV E04B 1/94 P

Claims (12)

[Claims] 1. A boric acid compound is mixed with either an aqueous solution of a sequestering agent or an aqueous solution of a wet penetrating surfactant so as to have a solubility equal to or higher than 5 g / 100 g of water at room temperature. A high-concentration boric acid compound obtained by hydrothermal reaction at a temperature of ℃ or higher. 2. A boric acid compound is mixed with either an aqueous solution of a sequestering agent or an aqueous solution of a wet-penetrating surfactant so as to have a solubility equal to or higher than 5 g / 100 g of water at room temperature. A high-concentration boric acid compound obtained by hydrothermally reacting at a temperature of not less than 0 ° C., and further adding either one or both of phosphoric acid and a silanol salt having a siloxane skeleton. 3. A boric acid compound is mixed with either an aqueous solution of a sequestering agent or an aqueous solution of a wet penetrating surfactant so that the solubility thereof at room temperature is 5 g / 100 g of water or more, and a weak acidity is added thereto. Alternatively, a high-concentration boric acid compound obtained by adding a weakly alkaline mineral acid salt and subjecting this mixture to a hydrothermal reaction at 60 ° C. or higher. 4. A boric acid compound is mixed with either an aqueous solution of a sequestering agent or an aqueous solution of a wet penetrating surfactant so that the solubility thereof at room temperature is 5 g / 100 g of water or more, and the mixture is weakly acidic. Alternatively, a weakly alkaline mineral acid salt is added, and this mixture is hydrothermally reacted at a temperature of 60 ° C or higher,
Furthermore, a high-concentration boric acid compound obtained by adding one or both of phosphoric acid and a silanol salt having a siloxane skeleton. 5. A fireproof / fireproof composition containing the high-concentration boric acid compound according to any one of claims 1 to 4. 6. A fireproofing / refractory composition containing the high-concentration boric acid compound according to claim 1 combined with a method of normal pressure injection, pressure injection or reduced pressure injection. A fireproof / fireproof material characterized by being obtained by impregnating wood and drying it. 7. A fireproofing / fireproofing composition containing the high-concentration boric acid compound according to claim 1, which is either a synthetic resin or a latex, and an isocyanate group or zinc oxide. Alternatively, it is mixed with a composition containing an isocyanate group or zinc oxide and mixed, and then coated or impregnated on any of textile products, wood chips, wood fiber products, paper products or inorganic sheet products,
Fireproof / fireproof material obtained by drying at room temperature or by heating. 8. A binder obtained by adding a thermosetting resin to the fireproofing / refractory composition containing the high-concentration boric acid compound according to any one of claims 1 to 4. 9. A fireproofing / refractory composition containing the high-concentration boric acid compound according to any one of claims 1 to 4 is applied, dipped or poured into a textile product, a paper product, or a wooden product. A fireproof / refractory material characterized by being obtained by subsequent drying. 10. A fireproof / refractory composition containing the high-concentration boric acid compound according to any one of claims 1 to 4 is applied to or mixed with a surface of a synthetic resin solid, a silicone resin or a fluororesin. A fire and fire resistant material that is kneaded and dried to make it highly heat resistant. 11. An inorganic or organic woven fabric or non-woven fabric is impregnated with the fireproof / refractory composition containing the high-concentration boric acid compound according to any one of claims 1 to 4, and this is semi-dried. Fireproof and fireproof material made of prepreg sheet or dried sheet mold compound. 12. A mixture of the fireproofing / refractory composition containing the high-concentration boric acid compound according to any one of claims 1 to 4 and either carboxymethyl cellulose or carboxymethyl hydroxyethyl cellulose, and an inorganic or Fireproof / fireproof material that is made by impregnating an organic woven or non-woven fabric and then semi-drying it, or using a dried sheet mold compound.