CN1122770A - Concentrated boric acid compounds and fireproof and fire-resistant composites containing the compounds, and binding materials, fireproof and fire-resistant materials formed by the use of the compounds - Google Patents

Abstract

A high concentration boric acid compound is characteristically obtained by mixing a boric acid compound with either an aqueous solution of a metallic ion sealing agent or aqueous solution of a wet permeable surfactant to reach a concentration of the compound above a solubility equivalent to 5 g/100 g water at normal temperature, subjecting this mixture to a hydrothermal reaction at >= 60 DEG C or further adding either or both of a phosphoric acid and a silanol salt having siloxane skeleton. And the flameproof/flame resistant material is produced by using a composition for flameproofing/flame resisting containing the high-concentrationed boric acid compound.

Description

High concentration of boric acid compound and fireproof composition thereof and fireproof material

The present invention relates to contain the fireproof composition of the high concentration of boric acid compound that can be applicable to the fireproof material down nuisanceless for increasing the weather resistance of timber and natural fiber, and the fireproof material that uses said composition.

In global environment, if with high-quality timber and durableization of natural fiber, and make non-harmful inorganic composite materials, then can produce weather resistance, and can constitute the fireproof material and prevent fire, even carry out recirculation, in the future that returns the earth, also can constitute the material that people expect, so they have wide application field.

On taking precautions against natural calamities, just seeking to make daily necessities and clothing, furniture, material of construction to become difficult combustion, and when fire, can not produce the fire-retardant material of obnoxious flavour and smog.Ball border on the spot, requirements of the times natural timber product and fiber, paper product must pest control and anticorrosions, and durable is saved resource.

Product of the present invention is owing to reaching these purposes, so utilized widely in every field.Can be applicable to the nuisanceless fire retardant of mass production synthetic resins.

Past is as the natural fiber of timber, kapok, a numb class, owing to there is not the cause of weather resistance, use the synthetic resin article in the petroleum product to replace, yet, when in a single day synthetic resin article runs into fire, cause public hazards owing to produce obnoxious flavour and dense smoke, institute thinks and prevents that this situation from mixing with fire retardant, and commercialization.This fire retardant has halogen compounds, P contained compound, nitrogen compound, and metallic compound or the like produces but still have gas when worrying burning.

Though the past is used the boronic acid compounds fire retardant as far as possible, must be made into diluting soln.Even used this diluting soln can not produce fire resistance.

In order to produce the fireproof performance, all can not there be meal to separate out when being normal temperature or during burning, just not can not tell on if be not coated with membranization yet, must add emulsion for this reason.Though but can make flame proof with this method but not prevent fires.Produce fire resistance in order to inject timber, must be on the exsiccant tissue surface the remaining solids of degree to cover.

As fire retardant, general used phosphoric acid or guanidine sulfate, but use them in large quantities for making fire-retardant material are then because of its injection with produce gas many problems are arranged.

Not firebrand of standard material is arranged as commodity selling on market, but make manufacturing engineering become not simple and easy, and the expense height.In matrix materials such as chipboard, MDF, asbestos plate, urea aldehyde (ュ リ ヤ) resin, melmac, resol etc. have been used.The concentration of contained synthetic resins is 40～65% in the product of market sale, in fact, uses though reduce concentration, and the concentration of contained synthetic resins is still about 40%.If in the fireproof matrix material, do not adopt above-mentioned concentration, just can not replace.

Up to ending to today, non-harmful inorganic solution is made the high density formed material of filming during burning also of no use.Can inject in timber and natural fiber and soak the material that contains must be the solution that can be injected in the fibrous tissue.The suspension liquid that use has particle can not produce useful effect.

That boronic acid compounds has is fungi-proofing, insect protected and mildew-proof function, and the effect with flame proof has been known, but owing to can not use high density, and can not be coated with membranization, so also just can not be applied in the fire-resistant fire-retardant material.The sanitas in past is even effectively can not make fire-retardant material to anticorrosion.

Commercially available fire retardant is blended in the synthetic resins, produces decomposition gas when fire, has the effect of fire extinguishing effect, extensively obtain using, even but have the effect of short period of time, and the flameproof effect that will for example keep more than 10 minutes also is very difficult.And in these decomposition gases, contain a large amount of nitrogen and chlorine of taking precautions against natural calamities of being unfavorable for.Organic or the resin of the liquid that uses in commercially available raw material, solid component concentration reaches 65%.When being converted into solubleness 65/35=1.857.Because the known solubleness of boronic acid compounds is 5%, if suitable, be necessary then to be made into that solubleness can not reach that 150～200% nothing is separated out and sedimentary stabilizing solution with 1.857 value.

For in synthetic resins, mixing, sneak into or sneaking into resin surface to film all can with fine powder.But no matter which kind of situation in order to make the dry body with useful effect, must be made the high density goods.

Seeking fireproof inorganic fiber composite product, but inorganic preimpregnation goods fail also to realize.The same therewith, also the sheet material or the molding composite wood of difficult burning can appear in hope.

The matrix material of timber and natural fiber must be neutral, tart.Cheap inorganic fire agent is boronic acid containing compound and phosphate cpd, but which kind of all can not make film separately.Borax and boric acid can not be made high density because of solubleness is low.Phosphoric acid can be made high density, but strong acid.

That is to say after the highly concentrated solution of having stipulated the boronic acid containing compound but there is not to adjust arbitrarily the method for pH value.In addition, the solution of boronic acid containing compound does not become solution because of temperature variation produces to separate out, moreover efflorescence during because of drying, can not make and film, so just can not constitute fire-resistant fire-retardant material yet.

Boronic acid compounds is water miscible owing to do not use solvent, thus when fire, do not produce harmful decomposition gas, again owing to being a kind of material that antiseptic insect-repelling is arranged, so also be low-cost goods.But shortcoming is that known boronic acid compounds solubleness (dissolving g/100 water, 20 ℃) is no more than 5%, can not constitute the high density goods.

As illustrating in this specification sheets, present inventors propose, and add more than one of metal ion end-capping reagent and the tensio-active agent with moistening impregnability, and phosphate cpd and silicon alkoxide, and heating constitutes the high concentration of boric acid compound compositions.

In the process that adds said mixture, can see that variation has taken place the crystal habit of boronic acid compounds.That is, when above-mentioned reaction soln is heated to high temperature, become appearance transparent solution, when using microscopic examination, still remaining crystal habit, thereby the reason that Here it is as can be known also separates out when adopting at normal temperatures.

Therefore, present inventors are clear and definite makes and does not separate out and sedimentary stable high concentration of boric acid compound water solution, and when drying amorphous means and the method that is coated with membranization.

The heat-resisting growth promoter that can improve the heat-resisting temperature of synthetic resins of polyolefin and polyethers, polyester system or their mixed stocker does not also occur, the existing commodity selling of the mixture of the high heat-stable material of admixture in low heat-stable material.So there are the goods of various grades, its thermal stability differs 10～20 ℃.

Various fire retardants are subjected to the fire retardant of rules and regulations restrictions or are subjected to the predetermined fire retardant of rules and regulations restriction in the future, but also find to replace they and non-harmful fire retardant.In addition, the insect protected protection against rodents mould inhibitor that produces decomposition gas under normal temperature or heating is arranged, but worry because of the gas that produces environment to be caused public hazards, hope is released has the goods that keeping quality does not produce obnoxious flavour again.As everyone knows, boronic acid compounds has Vermins-proof mildew-proof protection against rodents and other effect, but must make highly concentrated solution for widespread use.

For boronic acid compounds is made highly concentrated solution, the crystallization of borax boric acid must be refine to nanoscale size, latexization or be made into amorphous material.No matter use the metal ion end-capping reagent with the boronic acid compounds complex saltization, still use the tensio-active agent micellerization, their crystal habit still remains in the solution, knows the remaining problem that precipitation is arranged and separate out so still can declare.In addition, even add the complete refinement of crystallization that acid can not make boronic acid compounds, along with the variation of condition can become thick.Even it is heated, also be difficult to keep the solution of high density at normal temperatures, combine with aforesaid method with physics mode, perhaps carry out the refinement test with colloidal mill individually, make it be liquefied as trickle colloid, but will make amorphous material also is difficult to.This situation is shown in Figure 17 to Figure 19.

In practicality, use on the one hand for boronic acid compounds being made fire-resistant fire-retardant material.The composition that contains boronic acid compounds must have 100～300% solubleness, and it should be made desciccator diaphragm, and is dull and stereotyped or film.

Present inventors consider to adopt makes various materials be difficult to the incendiary gimmick, with its method with thermolysis gas removal oxygen in the past, not as filming to cover with heat it is not decomposed, and postpones heat conducting heat-absorbing action, solves.

Present inventors propose can to make timber and natural fiber reach standard with the composition that contains boronic acid compounds in the present invention and do not fire or be difficult to the incendiary degree.In this case, if highly concentrated solution can be accomplished a small amount of injection, fast drying, productivity height.

The means of above-mentioned synthetic resins being carried out difficult burning are, must the surface of solid part attached to synthetic resins with solution of the present invention on, perhaps this solution is made powdery and is mixed in the synthetic resins.But must drying remove residual moisture at low temperatures, must adhere in a large number for this reason, so the boronic acid containing compound compositions is necessary to make high density.In addition, in order to make fire-resistant fire-retardant material, the boronic acid containing compound compositions must be heat-resisting filming, and does not at high temperature decompose.And must have heat-absorbing action and effect.

That is, the boronic acid compounds of crystal form be that impossible to make solubleness be 100～300% solution according to the final conclusion in past, and at this moment, crystalline material will become amorphous substance, film thereby can form resistivity against fire.

The invention solves these problems.

First invention that inventors propose is a kind of high concentration of boric acid compound, it is characterized in that, in the metal ion end-capping reagent aqueous solution or moistening impregnability water phase surfactant mixture no matter any, mix boronic acid compounds in the mode that solubleness at normal temperatures is equivalent to more than the 5g/100g water, this mixture is obtained carrying out hydro-thermal reaction more than 60 ℃.Second invention is another kind of high concentration of boric acid compound, it is characterized in that, in the metal ion end-capping reagent aqueous solution or moistening impregnability water phase surfactant mixture be no matter any, mix boronic acid compounds in the mode that solubleness at normal temperatures is equivalent to more than the 5g/100g water, this mixture is being carried out hydro-thermal reaction more than 60 ℃, adding phosphoric acid in addition again or have silane alkoxide any of siloxane backbone or two kinds and obtain.The 3rd invention is another high concentration of boric acid compound, it is characterized in that, in the metal ion end-capping reagent aqueous solution or moistening impregnability water phase surfactant mixture be no matter any, mix boronic acid compounds in the mode that solubleness at normal temperatures is equivalent to more than the 5g/100g water, add slightly acidic or weakly alkaline inorganic acid salt again, this mixture is obtained carrying out hydro-thermal reaction more than 60 ℃.And the 4th invention is another high concentration of boric acid compound, it is characterized in that, in the metal ion end-capping reagent aqueous solution or moistening impregnability water phase surfactant mixture be no matter any, mix boronic acid compounds in the mode that solubleness at normal temperatures is equivalent to more than the 5g/100g water, add slightly acidic or weakly alkaline inorganic acid salt again, this mixture is being carried out hydro-thermal reaction more than 60 ℃, add phosphoric acid in addition again or have siloxane backbone the silane alkoxide one or both and obtain.

Have, inventors are as the 5th invention again, propose to contain any fireproof composition in the high concentration of boric acid compound of above-mentioned first to the 4th invention.

In above-mentioned, said " normal temperature " is 20 ℃, promptly, the solubleness of the boronic acid compounds that said " solubleness of boronic acid compounds is in 5g/100g water at normal temperatures " is such, mean that having solubleness to surpass is considered to known in the past, is equivalent to the situation of the solubleness of 4.7g/100g water under 20 ℃.

In above-mentioned, " carrying out hydro-thermal reaction more than 60 ℃ " is in order to improve the solubleness of boronic acid compounds.Temperature being taken as " more than 60 ℃ " is because more than 60 ℃, borax becomes insoluble five water and salts out, and this point is known, the objective of the invention is to want head it off, provide a kind of high concentration of boric acid compound, even do not separate out also not having boronic acid compounds more than 60 ℃.In addition, the temperature of carrying out hydro-thermal reaction preferably is decided to be 60 ℃～100 ℃.

In above-mentioned, utilize to add phosphoric acid or have in the silane alkoxide of siloxane backbone one or both, can at random between 4～8, adjust the pH value of high concentration of boric acid compound.

Present inventors propose to use fireproof material and the matrix material of the fireproof of the high concentration of boric acid compound that contains above-mentioned first to the 4th kind of invention with the following type of composition.

1. a fire-resistant fire-retardant material is characterized in that, will contain the fireproof composition of above-mentioned any high concentration of boric acid compound, the comprehensive normal pressure that adopts injects down, the method that pressurization is injected or decompression is injected immerses in the timber, more this timber is carried out drying and obtains.

2. fireproof material, it is characterized in that, any with synthetic resins or latex, with any of isocyanate group or zinc oxide or contain isocyanate group or the composition of zinc oxide carries out compound, mix mutually with composition with the fireproof that contains above-mentioned any high concentration of boric acid compound again, with its coated in fibre product, wood chip, wooden fine goods, paper product or inorganic plate-shaped products on any goods, perhaps soak and contain coating, under normal temperature or heating, carry out drying and obtain.

3. a matrix material is characterized in that, adds thermosetting resin and obtain in containing the fireproof composition of above-mentioned any high concentration of boric acid compound.

4. a fireproof material is characterized in that, the fireproof composition that will contain above-mentioned any high concentration of boric acid compound is at coating, dipping on fibre product, paper product or the woodwork or after injecting, and carries out drying and obtains.

5. a fireproof material is characterized in that, will contain the fireproof composition of above-mentioned any high concentration of boric acid compound, be coated on the synthetic resin solid thing, on silicone resin or the fluororesin surface, perhaps mix mutually, make its drying, carry out anti-high thermal treatment again and obtain.

6. fireproof material, it is characterized in that, the fireproof composition that will contain above-mentioned any high concentration of boric acid compound soaks and is contained on inorganic or organic textiles or the non-textile, is made into semiarid preliminary shaping flitch or exsiccant laminated die plastic compound.

7. fireproof material, it is characterized in that, to contain the fireproof composition of above-mentioned any high concentration of boric acid compound and any mixing in carboxymethyl cellulose or the carboxymethyl hydroxyethyl cellulose, it is soaked be contained on inorganic or organic textiles or the non-textile, be made into semiarid preliminary shaping flitch or exsiccant laminated die plastic compound.

The present invention is defined as the high density that is higher than known solubleness with borax or boric acid (to call boronic acid compounds in the following text), in the method for under preventing low temperature, separating out simultaneously, the tensio-active agent (the following tensio-active agent that claims simply) that has used metal ion end-capping reagent (to call sequestrant in the following text) and had the wettability impregnability.Have again, adjusting in the method for pH value of solution value arbitrarily, stipulate in shared alkaline borax, boric acid, phosphoric acid, condensed phosphoric acid, phosphoric acid salt or the condensed phosphate at least a more than.Even used above-mentioned sequestrant and tensio-active agent that above-mentioned boronic acid compounds is made solution, become the little micelle of ion, when carrying out drying, also can make its powdered.Present inventors adopt the way of mixing the silane alkoxide that contains siloxane backbone, and it is dried to films, and can powdered.Also can use alkoxide to replace above-mentioned silane alkoxide.

Present inventors are perhaps promoting solubleness to surpass in the method for known solubleness in the solubleness of adjusting the hydration adhesive composition, and using sequestrant is feasible (for example special public clear No. 444221 and special public clear 48-No. 40444).Inventors are willing to clear 48-No. 24658 the spy, clear 48-No. 9681 of special hope, clear 49-No. 25386 (speciallyying permit No. 1189741) of special hope, and in the later set invention, the sequestrant that is disclosed is hydroxycarboxylic acid, t-inosinic acid or their salt of classes such as the gluconic acid, citric acid, keto-earboxylic acid of the EDFA that is widely used.And clear and definite fluorochemical, chromium, zinc, boronic acid compounds, phosphate cpd and above-mentioned sequestrant also produce mutual enhanced effect and effect.Tensio-active agent with sequestrant effectiveness also can make water-soluble metal ion micelleization, has the effect of promoting solubleness.

Except above-mentioned sequestrant, also have NTA, EDTA-OH, DTPA, and other various sugar-acidses.Tensio-active agent of the present invention has element beyond the only carbonaceous or carbon of hydrophobic group, anion surfactant according to chain combination formation, with the many rings anion surfactant that on hydrophobic group, has used natural matter, also have the cats product that forms by alkylamine salt and quaternary ammonium salt, all demonstrate effective function and effect.Sequestrant of the present invention is not limited to above-mentioned kind, meltage can be increased to more than the known solubleness under all temps condition, and form the mixture of clear solution, can carry out the various uses that mix according to certain method with boronic acid compounds.

Among the present invention, the said silane alkoxide that contains siloxane backbone that dissolved ion micelle can be coated with membranization is the water-based of the previous invention of inventors, can make the mineral compound of film, open flat 4-No. 239079 and United States Patent (USP) No. 5049316 the spy, and on the books in corresponding therewith special fair 7-No. 365 and 7-No. 14801.These external 1991, among the EVALMAT of material technology the 9th volume and iron and steel institute's international conference in 1989 clearly record is arranged all.

That is, carrying out the so-called inorganic polymer of hydration synthetic by metal (silicon, aluminium, other metal) and mineral acid (sulfuric acid, phosphoric acid, boric acid, fluoric acid, nitric acid or their inferior acid) or inorganic acid salt and basic metal.The silane alkoxide that replaces mineral acid with ammonia is used to shorten the effect of residual flame time also within the scope of the invention.Have more than in addition and limit above-mentioned silane alkoxide, for example, can use the ethylsilane alkoxide and the alkoxide of ethanol modification.

The known solubleness of borax decahydrate salt is no more than 4.7g/100g water under 20 ℃, under 60 ℃, do not increase solubleness, separates out five water salt.Even boric acid, under 20 ℃, being 3.992g/100g water, is 40.2g/100g water (physics and chemistry dictionary P1260-1261 under 100 ℃, 1976), promptly can understand that from the known solubleness of boric acid, borax making strength of solution surpass 5% is impossibility under 20 ℃.The solids component of the synthetic resin solution of said present commercially available matrix material is to represent with weight % at total amount, for example, says 45%, if according to above-mentioned solubleness, 45/55g promptly becomes 81.8%, but the concentration of in fact using is about 40%.The solubleness that this value is converted into boronic acid compounds is 66.6%.

Inventors have carried out following test for whether the solubleness that confirms practical solids component 50g/100g (water) is possible.

To 250 portions of borax decahydrate salt, 250 parts of boric acid, add up to 500 parts, in 1000 parts of water, add measuring of various sequestrants and tensio-active agent and be under 20 parts the preparation condition and carry out solubility test.Above-mentioned additive is added to the water, after being heated to more than 30 ℃, add the mixture (to call the boronic acid containing compound in the following text) that contains above-mentioned borax boric acid again, continue to be heated to the boiling temperature of top temperature under the normal pressure, be cooled to 20 ℃ again, viewed result is following situation.

Use citric acid, the xitix of hydroxyketone carboxylic acid, the Sodium Inosinate of nitrogen compound, the ion end-capping reagent of hydroxycarboxylic acid to be edetate (EDTA) as the representative candidate of above-mentioned additive.As anion surfactant, use the horizontal sour sodium (F-25) of dodecylbenzene, sodium alkyl naphthalene sulfonate, (NB-L), dialkyl sodium sulfosuccinate, alkyl diphenyl ether disulphonic acid sodium (SSL), special carboxylic acid type (ASK), naphthalene sulfonic acidformaldehyde condensation product sodium salt (NBL), special aromatic sulphonic acid formaldehyde condensation products sodium salt (SS-L), special polyocarboxy acid type polymer (PS.520).As cats product, use stearylamide acetate (86), stearyl-alkyl dimethyl ammonium chloride (D86P).

Which kind of no matter uses, under above-mentioned preparation condition, become clear solution, the liquid temperature reaches 35 ℃, and keeps this situation, separates out few.In the residual gross weight of heating evaporation, hydration is residual separates out when stating NBLASK in the use, demonstrates that the highest amount of separating out is about 25% under 20 ℃, and other is in 15%, and keto-earboxylic acid demonstrates highest solubility in 10%.Promptly 33.8～43.1g/100g water is on known solubleness.Under above-mentioned 20 ℃, the pH value is about 7, even change the preparation ratio of borax, boric acid, the pH value is also adjusted arbitrarily in 4-8 scope.

Be contained in can powdered when carrying out drying on the textiles when above-mentioned solution is soaked.Yet, can produce fire resistance if sneaking into 10 parts of (weight) emulsions films.

The present inventor according to the mixing step of additive, is coated in this solution on the sheet glass in above-mentioned test, and what see drying films.Observing uses the hydroxyketone carboxylic acid as the sequestrant example respectively, the variation of the stearylamide acetate (SAA) that uses the alkyl naphthalene sulfonic acid (NBL) of negatively charged ion series and positively charged ion series crystal habit during as the tensio-active agent example remains on the 500cc aqueous solution more than 80 ℃ and to observe.Take pictures with microscope and to amplify 25 times, amplify 20 times with video again, add up to and amplify 500 times, it the results are shown in accompanying drawing 17～19.Situation when Figure 17 is to use hydroxycarboxylic acid, the situation when Figure 18 is to use alkyl naphthalene sulfonic acid, Figure 19 is to use the situation of stearylamide acetate.

In each figure, (a) be situation when having mixed 200g borax (to call BN in the following text), (b) be to keep under the situation of (a), situation when respectively mixing 2g sequestrant and tensio-active agent again, situation when (c) being mixing 100g boric acid (to call BA in the following text), (d) be to keep under the situation of (c) situation when having mixed 20g phosphoric acid (purity 89%) again.

Observations is found the crystalline material granular, forms netted combination, and become be coated with membranaceous.

Therefore, present inventors become amorphous substance to the crystalline material that makes boronic acid compounds again, and stable colloidal solution is studied.

Make borax and boric acid become the aqueous solution separately or, to boiling, the variation of grown form can not take place in no matter heated and stirred, or tinyization of crystal habit, can not granular from normal temperature with mixing.

The sequestrant with EDTA and NTA one class, citric acid and 2 ketone gluconic acids during this has been proposed a plan, contain the t-inosinic acid of nitrogen and phosphorus, the picture hydroxycarboxylic acid, or in negatively charged ion and positively charged ion and neutral tensio-active agent and ethylene glycol and polyethers (PPGPTMEGPTG) the blended water, be mixed into boronic acid compounds, stirring heating, even by colloidal mill, still exist in the BORAX PENTAHYDRATE-99.9 MIN salt crystallization that generates more than 60 ℃.

No matter be to add phosphoric acid, nitric acid and sulfuric acid in the sodium salt with borax to form sodium salt, still change crystal habit, all can not reach granular, the crystallization meeting is reverse as can be known becomes thick according to condition.

According to above observation, be necessary the katalysis or the coupling that promote that crystallization changes.In above-mentioned condition, when from slightly acidic or weakly alkaline an alkali metal salt, for example, select in Sodium Fluoride (pH7.74), sodium phosphite (pH7.02), S-WAT (pH9.87), Sodium Nitrite (pH9.04), the boron Sodium Fluoride (pH6.2), when mixing, become solution easily.Basic metal can all use Na, K, Li.

Wish that this dry coating becomes glassy or membranaceous material, and can't see the crystal habit of boronic acid compounds, the salt of above-mentioned sequestrant and tensio-active agent is preferably 1 valency salt.

In above-mentioned cooperation, when the phosphoric acid that adds 1-20 parts heavy 85-89%, pH can adjust arbitrarily in 4-8.And improved the problem of separating out under the low temperature.Be used for the phosphoric acid that pH adjusts, have more than and be defined in ortho-phosphoric acid, contain condensed phosphoric acid and their salt, and have the alkaline sequestering action and the effect of borax.When cotton being flooded in these liquid and when dry, can improving some saturating film properties.

Use above-mentioned sequestrant and tensio-active agent, what is called has been dissolved boric acid, borax, can have been thought the ion micelleization, associated.When above-mentioned silane alkoxide with siloxane backbone is used for this matrix material, makes film properties and improve.

When mineral acid is boric acid in above-mentioned cooperation, if (Si, B, 20% solution, 1-30 weight parts Na) continue to mix with phosphoric acid, then can improve the fire-resistant performance of making film with above-mentioned silane alkoxide.In above-mentioned cooperation, in the solution of the present invention (being called PHN later on) of the above-mentioned silane alkoxide that has mixed 5 parts of weight, soak the non-spinning paper of glass (ペ-パ-) of 100g/m2, and carry out drying.To the goods of such processing and the product that are untreated, carry out flame resistance test.Being to test on 900 ℃ the burner at tip temperature, is when being untreated product, has just burnt the hole in 1-2 seconds, and item for disposal then wanted for 15 seconds, and this has just produced fire performance to a certain degree.

The pH value of above-mentioned PHN solution is adjusted to 5.8, and mixing 20% concentration is 60% melmac, and obtains matrix material.In 100 parts heavy this matrix materials, mix 200 parts of old newspaper paper pulp, under 140 ℃, carry out hot pressing, do not having to carry out heat embrittlement under the hardening catalyst.

When above-mentioned silane alkoxide being mixed when too much, obtain cellular complex body pottery.

On the other hand, with the mineral acid of above-mentioned silane alkoxide, for example, be taken as HNO ₃When (Si, NO, Na), can become needle crystal.

In the above-mentioned reaction,, just do not add the mineral compound solution that other mineral acid except that phosphoric acid and water-based are made film properties, can become the highly concentrated solution of boronic acid compounds yet as long as become highly concentrated solution simply.One of this purpose is made fire-resistant fire-retardant material with solution of the present invention exactly.For this reason, at high temperature must not decompose and left behind.

Present inventors proposed in the past, when adding water-based when making the film properties inorganic solution, the high concentration of boric acid compound solution of above-mentioned boronic acid compounds and tensio-active agent, inorganic acid salt can be carried out stabilization, became the fireproof material.The reason of its existence can obtain explanation according to back DTA-TG and FTIR analytical results.

The raw material of solution of the present invention, owing to be that pH is that about 9 borax and pH are about 5 boric acid, according to using proportioning can adjust the pH value that generates solution.By weight, the Na of borax composition ₂B ₄O ₇If surpass the H of boric acid component ₃BO ₃, pH can be higher than 7, if boric acid component is many, pH can be lower than 7.

Utilize microscopic examination can confirm effect of the present invention and effect.To gather dicarboxylic acid series of surfactants CAD-600 (Kao Corp's system), according to said ratio 20g/1000cc water, add each 250g borax, boric acid, add up to 500g, be coated in when observing on the sheet glass, calcite type at random and oblique system column crystallization are arranged.In dry thing, can see block crystallization.Then, mixing when admixing 50g phosphoric acid, is core with the boronic acid compounds, and needle crystal is gathered into pin chestnut shape.Mix the above-mentioned silanol salts solution that contains (Si, B, Na) of admixing 100g 7% more inwards.It is transparent that solution is, but when observing after drying, the crystallization before mixing has become glassy amorphous substance, observes non-textile and melting and be combined into the netted membrane stage that is coated with at random.By other condition, become filament crystal and ginkgo is lobate, the crystallization of knot shape becomes that composite-like is netted films again.

Promptly, in sequestrant of the present invention, form unsetting plate crystal if add borax boric acid, use above-mentioned phosphoric acid to form a lot of short palisade crystallizations, form mesh bonded parent form, when adding above-mentioned silane alkoxide, form the compelx coating at random as the synthetic resins non-textile of adhere, but can be observed with microscope.

The invention described above solution (PHN) is injected the China fir material to be tested.Use returns キ Star チ Application Ha ウ ス strain formula to understand all, and the timber injection device of assistant rattan ironworker manufacturing injects in conjunction with normal pressure, decompression, pressurization.Because above-mentioned boronic acid compounds PHN solution is clear solution, injection rate can reach the theoretical value of approximate China fir material weight 280%.This material is carried out JIS fire prevention test, heat test in 6 minutes, TD θ is 100, and CA is no more than 6.Promptly obtain 3 grades of qualified good results of the difficult combustion of JIS.

The non-textile of the fiber crops that 5mm is thick (ト コ ス Co., Ltd. system) carries out heat hardening and is shaped after the boronic acid containing Compound P HN solution of above-mentioned use and 60% melamine (three and ケ ミ power Le Co., Ltd.) flooded in the composite solution of proportioning by 80: 20 under 130 ℃.This goods burn with easy burner, do not produce flame, only carbonization.Adopt and use the same method, above-mentioned PHN solution is made matrix material, after with old newspaper fiber solidifying formation, carry out heating fire prevention test in 20 minutes, obtain being bordering on the test-results of 2 grades of the difficult combustions of JIS.

The latex solution of military field system 45% is adjusted to 10%, and adds the mixed solution that 3% special isocyanic ester forms, add in the PHN solution, with this solution coating on cotton, the result is even catch fire the burning of also can not stretching, demonstrate difficult combustion effect, and produced washing resistance performance.

Linking agent between PHN of the present invention and the latex mixed solution can use thermosetting resin and sulphur, and methylated methylol melamine is effective especially.

Use zinc oxide to replace above-mentioned isocyanic ester, coating on paper when normal temperature hardens down, produces caoutchouc elasticity, is difficult to burning.When paper is made the aluminum oxide silicon oxide thin plate of 1mm, improved the shortcoming of thin plate splitting resistance difference, and nonflammable.

Known solubleness at 20 ℃ of following boronic acid containing compounds is about 5%, but is more than 70% according to the present invention, if be higher than 50 ℃, might solubleness be 120g/100cc water.The lysate pH of borax is about 9, and the lysate pH of boric acid is about 5.But the present invention has the effect that the pH value of solution value is adjusted arbitrarily between 5-8.

In the present invention, because the highly concentrated solution of boronic acid containing compound has been made transparent liquid, can inject 1 micron conduit of timber, simultaneously, because drying becomes and films, do not have to change the drying when once injecting to this day, timber has kept the surface of natural true qualities, has produced the effect that can reach 2-3 grades of timber of the difficult combustion of JIS.When natural product paper and Cotton and Linen soak contained solution of the present invention after, becoming is difficult to burning, can strengthen resistance toheat to glass, asbestos, inorganic fibre goods.Moreover, highly concentrated solution of the present invention is owing to the matrix material that has become as synthetic resins, when making the matrix material of the difficult chipboard that fires, veneer sheet, MDF, paper forming product, can not produce combustion gases and smog, become and be difficult to the incendiary goods.

Carry out following improvement again, the result can make and adopt prior art can not obtainablely have boronic acid compounds up to 100-300% solubleness.

In water, stir sequestrant and tensio-active agent even add, know in the time can not being dispersed into uniform colloidal, just can not produce fabulous effect and effect yet.Found with above-mentioned weakly alkaline and weakly acidic Sodium Fluoride, sodium phosphite, S-WAT, Sodium Nitrite, boron Sodium Fluoride then to have the effect of the colloidal of being dispersed into to join in sequestrant and the tensio-active agent less than half weight.In sequestrant and tensio-active agent, add above-mentioned acidulous material and weakly alkaline material earlier, add borax thereafter, when adding boric acid again, it is membranaceous to form glass.After adding sequestrant and tensio-active agent and borax, perhaps add above-mentioned acidulous material or weakly alkaline material simultaneously, when adding boric acid again, the crystallization of boronic acid compounds is become be coated with membranaceous.By this effect, the solubleness that can realize the boronic acid compounds that can't reach by the end of today is up to 100-300% highly concentrated solution.

It is the silane alkoxide that the previous water-based that proposes of present inventors is made the film mineral compound, but amount (solids component adds more than 5% of boronic acid compounds) will produce fire performance as long as add seldom in boronic acid compounds of the present invention.Consider that this is based on being used of multiple composition.

The China fir of 15mm * 200mm * 300mm put into 40% PHN solution of the present invention is housed (container of NF-MH) is after reducing pressure, with 20kg/cm ²Pressurization is injected, and can confirm that by injection rate be 630 liters/m ³Ratio, after the drying, the residual quantity of solid part is 250kg/m ³, use Japan's smart mechanism fire prevention trier to carry out accurate non-combustibility test.Obtain TD θ 37, CA6, the achievement of Af18sec.

When adding carboxymethyl cellulose (CMC) more than 0.1% and carboxymethyl hydroxyethyl cellulose (CMHEC),, can both produce heat-stable composite performance even organism also has no relations.

At 125g/m ²Flaxen fiber on coating added the 20% above-mentioned PHN of 1%CMC (solution of NF-MF) also carried out drying.Use the burner of 1000 ℃ of front ends to burn,, also can not burn out even in flame, become crimson look.Can at random mix thermosetting resin in the solution of the present invention as the plain resin of urea, melmac, resol one class.

Therefore, solution of the present invention soaked be contained on glass fibre and the carbon fiber (have more than and limit these), with fully inorganic, or and above-mentioned thermosetting resin share, form the preliminary shaping flitch of the unreacted state that moisture entrapment gets off, can the heat drying sclerosis be shaped.

The formation material of filming of the invention described above owing to have B-O (postscript is FTIR) reactive group, has the mixed performance with synthetic resins, and this synthetic resins has ether, ester bond, owing to have heat-resisting and heat-absorbing action, and becomes and diverse nonflammable material in the past.

With PP (Mitsui petroleum chemistry system) and solid component concentration is that (solution of NF-MF) carries out equivalent weight to be mixed, and dried ester moulding performance can not change common shaping (Japan テ ス ト ラ ボ ミ Le test-results) for 30% PHN of the present invention.In difficulty combustion HB test, with respect to common goods 1 minute and 50 seconds, the present invention was 5 minutes and 10 seconds, demonstrates to have the thermotolerance performance.When sneaking into the solid powder of the above-mentioned PHN goods of the present invention of 50 parts of weight for PP, the HB test becomes 6 minutes and 30 seconds.

Also can work effectively to the alkene series that is considered as difficulty in the past.Use extrusion machine to be made into thin plate, make glasscloth and veneer sheet, reprocessing shaping SMC can be a safety helmet with this thin plate hot compacting.

Fig. 1 represents the differential thermal analysis of utilizing the combination of Sodium Fluoride (NF)-fluorinated silane alkoxide (MF) to make goods of the present invention (result's the figure of DTA-TG).

Fig. 2 is the goods of the present invention that represent among Fig. 1 to be analyzed at normal temperature (20 ℃) figure of FTIR down.

Fig. 3 is the goods of the present invention that represent among Fig. 1 to be analyzed figure at 400 ℃ of following FTIR.

Fig. 4 is the goods of the present invention that represent among Fig. 1 to be analyzed figure at 800 ℃ of FTIR.

Fig. 5 represents sodium phosphite (NP) and the mineral acid of silane alkoxide is made up as the mineral acid (MP) that uses sodium phosphite, and makes differential thermal analysis (result's the figure of DTA-TG) of goods of the present invention.

Fig. 6 is the goods of the present invention that represent among Fig. 5 to be analyzed at normal temperature (20 ℃) figure of FTIR down.

Fig. 7 is the goods of the present invention that represent among Fig. 5 to be analyzed figure at 400 ℃ of following FTIR.

Fig. 8 is the goods of the present invention that represent among Fig. 5 to be analyzed figure at 800 ℃ of following FTIR.

Fig. 9 represents Sodium Nitrite (NO) and the mineral acid of silanol is made up as the mineral acid (MO) that uses Sodium Nitrite, and the differential thermal analysis of the goods of the present invention that make (DTA-TG) is figure as a result.

Figure 10 is the goods of the present invention that represent among Fig. 9 to be analyzed at normal temperature (20 ℃) figure of FTIR down.

Figure 11 is the goods of the present invention that represent among Fig. 9 to be analyzed figure at 400 ℃ of following FTIR.

Figure 12 is the goods of the present invention that represent among Fig. 9 to be analyzed figure at 800 ℃ of following FTIR.

Figure 13 be represent S-WAT (NS) and the mineral acid of silane alkoxide as the mineral acid (MS) that uses S-WAT, make up and make the differential thermal analysis (figure as a result of DTA-TG) of goods of the present invention.

Figure 14 is the goods of the present invention that represent among Figure 13 to be analyzed at normal temperature (20 ℃) figure of FTIR down.

Figure 15 is the goods of the present invention that represent among Figure 13 to be analyzed figure at 400 ℃ of following FTIR.

Figure 16 is the goods of the present invention that represent among Figure 13 to be analyzed figure at 800 ℃ of following FTIR.

Figure 17 represents crystal habit variation diagram in boronic acid compounds and sequestrant (hydroxyketone carboxylic acid) mix stages.

(a) be the figure that represents when mixing 200gBN.

(b) be figure when being presented in remix tensio-active agent in (a).

(c) be the figure that represents when mixing 100gBA.

(d) be figure when being presented in remix phosphoric acid in (c).

Figure 18 represents crystal habit variation diagram in boronic acid compounds and tensio-active agent (alkyl naphthalene sulfonic acid) mix stages.

(a) be the figure that represents when mixing 200gBN.

(b) be figure when being presented in remix tensio-active agent in (a).

(c) be the figure that represents when mixing 100gBA.

(d) be figure when being presented in remix phosphoric acid in (c).

Figure 19 represents crystallization formation variation diagram in boronic acid compounds and tensio-active agent (the hard esteramides acetate) mix stages.

(a) be the figure that represents when mixing 200gBN.

(b) be figure when being presented in remix tensio-active agent in (a).

(c) be the figure that represents when mixing 100gBN.

(d) be figure when being presented in remix phosphoric acid in (c).

Figure 20 represents solids component at the goods of the present invention (130#) more than 20% and the solids component crystalline state figure at the goods of the present invention (140#) more than 30%.

(a) be to represent 130# is carried out the state graph that amorphous substance is coated with membranization.

(b) be to represent the state graph of 130# being carried out the coating of wood tissue.

(c) be to represent 140# is carried out the state graph that amorphous substance is coated with membranization.

(d) be to represent the state graph of 140# being carried out the coating of wood tissue.

Figure 21 represents crystal habit variation diagram in the goods generation phase of the present invention of NF-MF type.

(a) be to represent blended state graph in water with EDTA.

(b) be to be presented in the state graph that mixes NF in (a).

(c) be to be presented in the state graph that mixes borax in (b).

(d) be to be presented in the state graph that mixes boric acid in (c).

(e) be to represent the state graph that in (d), mixes MF again.

Figure 22 represents crystal habit variation diagram in the goods generation phase of the present invention of NF-MF type.

(a) be to be presented in the state graph that mixes NBL in the water.

(b) be to be presented in the state graph that mixes NF in (a).

(c) be to be presented in the state graph that mixes borax in (b).

(d) be to be presented in the state graph that mixes boric acid in (c).

(e) be to represent the state graph that in (d), mixes MF again.

Employing following examples describe.

Embodiment 1

Using US-built purity is the borax decahydrate salt of 99% above grade and the phosphoric acid of boric acid and 89% (peaceful chemistry system), carries out following experiment.In 1000cc water, select to add 5g, 10g, 20g, 30g, 40g, 50g EDTA2Na, carry out mixed dissolution, be heated to 30 °～60, mix each 250g of borax boric acid and add up to 500g.When the EDTA combined amount is 5g, under 30 ℃, still have not dissolution residual substance, when reaching more than 80 ℃, all dissolvings, in other addition, under 30 ℃, dissolution residual substance does not reduce to some extent, but in all dissolvings more than 60 ℃.Yet, when solution temperature is lowered into below 35 ℃, begin to separate out, during 20 ℃ the maximum amount of separating out, separate out 10% of gross weight.That is, obtain the above solubleness of 35g/100cc.Heating once again needs the temperature more than 70 ℃ when reaching whole dissolving.

Embodiment 2

The sequestrant of the foregoing description 1 is replaced into citric acid and the xitix (keto-earboxylic acid) and the Sodium Inosinate of hydroxycarboxylic acid, carry out same experiment.More than 75 ℃, all dissolvings, but separate out 15～25% of total amount at 20 ℃.Promptly become the above 13～28g/100cc water of known solubleness.

Embodiment 3

Use following anion surfactant or cats product to replace the EDTA of the foregoing description 1, carry out same experiment.

As anion surfactant, use SS-40N (soap, Kao Corp's system), Ai Maer 71 (alkyl sulfuric ester), the tired gram of Nei Wopai this 25 (Sodium dodecylbenzene sulfonate), shellfish Simon Rex NB-L (sodium alkyl naphthalene sulfonate), shellfish Simon Rex OT-P (dialkyl sodium sulfosuccinate) shellfish Simon Rex SS-L (alkyl diphenyl ether disulphonic acid sodium), ラ テ system Le WX (polyoxy ethyl sodium alkylether sulphate), ラ テ system Le ASK (special carboxylic acid type negatively charged ion), DEET ointment NL (β-naphthalene sulfonic acidformaldehyde condensation product sodium salt), DEET ointment SS-L (special aromatic sulphonic acid formaldehyde condensation products sodium salt), diethylmethyl acid amides ointment EP wins Yi Si 521 (special polyocarboxy acid type polymeric anion), ethylene glycol, polypropylene glycol.

As cats product, use A Saitaming 86 (stearylamide acetate), コ- ミ Application 24P (Dodecyl trimethyl ammonium chloride), ア Application ヒ ト-Le 24B (lauryl betaine).

No matter when any, all at 60 ℃～90 ℃, the solubleness that obtains boric acid borax mixture is 50g/100g water more than known.

Yet,, separate out 20～25% of total amount below 20 ℃.

Embodiment 4

The special poly carboxylic acid tensio-active agent WH-Z and the CAD-600 of Kao Corp's system of using in the mixture at gummed replace the EDTA of embodiment 1 respectively.Under 50 ℃, above-mentioned boronic acid compounds 10% dissolution precipitation not of having an appointment, but add then all dissolvings of phosphoric acid (for water 5%, for boronic acid compounds 10%) of 50g above-mentioned 89%.

Embodiment 5

Use used in the above-described embodiments poly-dicarboxylate CAD-600, experimentize, show borax solubleness 1000g/1000g water.With CAD-600 100g in water, mixing with borax ratio 10%, even be heated to 60 ℃, BORAX PENTAHYDRATE-99.9 MIN salt also produce do not dissolve residual.In adding 100g the foregoing description, during used 89% phosphoric acid, become clear solution.Under 20 ℃, see small amount of precipitate.Produce subsequently and separate out.

Embodiment 6

" the forming the gummed mixture material by special anhydrite " of making according to the invention of No. 1189741, above-mentioned patent has the dissolved effect of promotion and effect, and it is to mix 1g Calcium Fluoride (Fluorspan), the dihydrate gypsum that burns till under 750 ℃ in the 100g gypsum.Use above-mentioned anhydrite 10g (CaF2/ boronic acid compounds=0.02%) and replace the EDTA of 20g the foregoing description 1 as the citric acid 2g (2g/500g, 0.4%) of sequestrant.When being warming up to 80 ℃, boronic acid compounds all dissolves.

Embodiment 7

Borated compound dissolution degree is become 70g/100g water, and the adjusting arbitrarily between 5.5～9 of pH value, the implementation process for preparing clear solution below shown.

The special polycarboxylate マ イ テ イ-WH-Z that in 10kg water, mixes the above-mentioned Kao Corp of 300g system.PH is 8.85.Be 99% borax decahydrate salt to wherein mixing the above-mentioned US-built purity of 1.2kg again.PH is 8.9.Even be heated to 50 ℃, still have undissolved residue.

Mix the phosphoric acid of 500g 89%, the pH value becomes 4.98 under 68 ℃, and dissolution residual substance does not no longer exist.

Mix therein again 500g 23% contain by コ-ミ ッ Network ス Co., Ltd. system by (Si, B Na) during the silanol solution of the siloxane backbone that forms of element, become clear solution, and under 56 ℃, pH is 5.27.Continue heating on one side, Yi Bian again to the boric acid that wherein mixes 2kg US-built 99%, under 72.8 ℃, pH is 3.12, remix 500g boric acid, the pH value becomes 3.08.Mix the borax of the above-mentioned demonstration alkalescence of 3.3kg, the pH value becomes 5.38.More than 50 ℃ transparent liquid.

Make the boronic acid containing compound solution that solubleness is 70g/100g water this moment.

Embodiment 8

Use the solids component assay method of heating in 105 ℃ * 3 hours, solids component is become (130#) and solids component become (140#) more than 30% 20% or more, according to following proportioning, 80 ℃ of inner edge heating edge adjustment.

130# 140# water 100kg 100kgWH-Z 1.2 CAD 6 boraxs 22 boraxs 35 boric acid 18 boric acid 35 phosphoric acid 5.4 phosphoric acid 7.5MH 5 MH 2.5

151.6kg 105 ° * 3H of ratio＞20% solids component of 186kg boronic acid containing chemical combination 40/,100 70/100 things＞30% solids component pH 6.5 6.2

In the said ratio example, adopt the method that has increased phosphoric acid amount, the pH value can easily become 4.For improving the pH value, if increase the borax ratio in borax/boric acid proportioning, no matter pH can be adjusted to is 7 or 9.Phosphoric acid has more than and is defined as ortho-phosphoric acid, regulates the result even use condensed phosphoric acid also can obtain same pH value.That is, the cooperation ratio of change borax boric acid phosphoric acid can implement to set arbitrarily the pH value.

According to the clear solution (130# and 140#) of above-mentioned acquisition, utilize microscope photographing to amplify 25 times photo their crystalline texture about respectively, amplify 20 times with video again, add up to and amplify 500 times, observe (Figure 20 (a) and (b), (c), (d)).(a) be that 130# is carried out the state that amorphous substance is coated with membranization, (b) being that 130# is injected timber, at the film forming state of its tissue surface shape, is that 140# is carried out the state that amorphous substance is coated with membranization (c), (d) be that 140# is injected timber, at the film forming state of its tissue surface shape.

Use above-mentioned transparent liquid, inject the timber experiment.

* use the made 0.6m diameter * 4m of machine assistant rattan ironworker

* the sapwood proportion 0.358 of timber Kingsoft China fir

Water ratio 11.5%

* condition A. decompression-750mm Hg is 30 minutes

B. reduce pressure 120 minutes hold-times

C. 60 minutes normal pressure hold-times-50mm Hg

D. 30kg/cm pressurizes ²480 minutes

E. pressurize 5 minutes hold-times

F. bushing temperature is 50 ℃

* the result 1) injection rate 874kg/m ³

(mean value) 2) weight impregnation rate 244%; 3) volume impregnation rate 244%

4) space impregnation rate 93%

This material is following dry 48 hours at 60 ℃.Not distortion.

The test body has natural surface color, nondiscoloration, appearance looks elegant.

These test bodies at the industrial technology center, are carried out surface and test according to build economizing regulation in No. the 3415th, the bulletin, below the results are shown in.

The residual flame of TD θ CA

3 grades of 2 grades 3 grades 2 grades benchmark＜250＜100＜120＜60＜30 second 130# 105 8 28140# 100 5 25

Embodiment 9

The solids component of top embodiment 130#, the mensuration through 105 ℃ * 3 hours is 21.2%.When mixing, mixing the back solids component respectively becomes about 30% with the melamine of its 80 parts and 20 part 60% (three and ケ ミ power Le society).The non-textile (ト ス コ Co., Ltd. system) of 7mm fiber crops is flooded in above-mentioned PHN solution, remainder is dewatered, under 130 ℃, carry out heat embrittlement.

Because employed tensio-active agent has carboxyl, under catalyst-free, can harden in 10 minutes.

Carry out the fire-retardant material test identical with top embodiment, the test-results of acquisition meets 3 grades of the difficult combustions of JIS.

With 2 times of above-mentioned solution with water dilutions, carry out same dipping, drying, also can obtain to meet the test-results of 3 grades of the difficult combustions of JIS.

Embodiment 10

Old newspaper is starched 1kg (ten system made of paper) flood in the PHN melamine mixed solution of embodiment 9 in the above, the centrifugal residual solution that removes becomes paper pulp: mixed solution=1: 2, with its 150 ℃ down heating carried out heat embrittlement in 10 minutes and be shaped.Carry out the alcohol combustion test by rolling stock in Japan association in mechanical technology regulation, the result is that flame, residual flame, vestiges are caught fire, to the thick nothing of 15mm, and carbonization length is 85mm below the 100mm of regulation, obtains the test-results corresponding to non-fire material.

Embodiment 11

The numb non-textile that 10mm is thick (ト ス コ Co., Ltd. system) floods in the solution of 2 times of the PHN melamine mixed solution dilute with waters that will go up embodiment 9, and squeezing and twisting the back result is fiber crops: mixed solution=100: (350～400).With it after 130 ℃ of down dry sclerosis are shaped.Be white in color, have flexibility,, only produce carbonization even have on welding fusing spark falls, and missing of ignition seeing through.

Embodiment 12

Change the melamine in the foregoing description 9, add oleic series, phenylethylene, rubber series latex (military field system) respectively and add 10% above-mentioned mixed solution in the urea resin solution of making, remix 1% zinc oxide is modulated into 3 kinds of liquid.In these liquid, flood 100g/m ²Cotton.After treating its drying, the field system isocyanic ester of useing force is handled.That acquisition has a washing fastness and promptly use the also non-ignitable flame retardant property of burner.

Embodiment 13

The EDTA that mixes 10g 40% in 500cc water is 80 ℃ of heating down.Utilize microscope photographing to amplify 25 times of photos it, under video, amplify 20 times again, add up to and amplify 500 times, when observing, do not reach homodisperse (Figure 21 (a)).

Add 3g Sodium Fluoride (bridge originally changes into system, to call NF in the following text) therein and stir, obtain homodisperse (Figure 21 (b)).

Add 230g borax decahydrate salt (USA makes purity 99%) more therein and continue to heat while stirring, random inspection, crystallization be panelized (Figure 21 (c)).

When adding 135g boric acid (USA system, purity 99%) continuation stirring again, its dry coating forms glassy filming, and does not find that there be (Figure 21 (d)) in crystallization.

The fluorinated silane alkoxide solution of being made by Pure Silicon Metal, Sodium Fluoride and caustic soda (コ of Co., Ltd.-ミ Star Network ス system is to call MF in the following text) that adds 30g 7% again when adjusting, under normal temperature (20 ℃), does not all have precipitation and separates out (Figure 21 (e)).Under Figure 20 ℃ state, pH is 7.2.

Replace above-mentioned EDTA with NBL, carry out and above-mentioned identical observation.With the above-mentioned identical stage in, same, photograph photo with microscope, observe.It is presented among Figure 22 (a) and (b), (c), (d), (e).

Embodiment 14

The solution of embodiment 13 is dried to Powdered under 150 ℃, contains moisture 5%, according to it DTA-TG and FTIR at 20 ℃, 400 ℃, the analytical results under 800 ℃ is (to call NF-MF), be shown in Fig. 1 to Fig. 4 in the following text.

Adopt DTA-TG, even reach more than 800 ℃, changes in weight also seldom demonstrates and continues the heat absorption phenomenon.According to FTIR, near 3450cm ^-1Water molecules, do not disappear even be heated to 800 ℃ yet, have heat-absorbing action and effect, at 1400cm ^-1Near B-O vibration changes with heating, near 1065cm ^-1Even silanol group reach a high temperature and also do not disappear, still remainingly get off.

That is, for fire-resistant fire prevention, the existence of above-mentioned fluorinated silane alkoxide (water-based is made the film mineral compound) is necessary.

Embodiment 15

Replace the Sodium Fluoride among the embodiment 13 with sodium phosphite (to call NP in the following text), Sodium Nitrite (to call NO in the following text), S-WAT (to call NS in the following text), correspondingly substitute the mineral acid of above-mentioned silane alkoxide (MF), use under the occasion of phosphoric acid class (Si, P, Na) (to call MP in the following text), nitrose (Si, NO, Na) (to call MO in the following text), sulfuric acid based (Si, S, Na) (to call MS in the following text), observe DFA-TG, the FTIR identical with embodiment 14.The result is presented in Fig. 5～Figure 16.

No matter in which kind of situation, or more than 800 ℃, all do not decompose, weight reduces also fewly, still remaining have the strong alkyl and a peak of silanol group.This proportioning can be regarded and add the boron Sodium Fluoride as on the chemical ingredients and be served the same role.

Embodiment 16

In the aforementioned embodiment, when borax 15g, boric acid 10g, tensio-active agent and sequestrant are the 0.3g of boronic acid compounds more than 1%, if inorganic acid salt also is its 0.25g more than 1%, then, even lack above-mentioned silane alkoxide, also can become the boronic acid compounds clear solution more than the known solubleness 5g/100g water of boronic acid compounds.

Embodiment 17

In 500cc water. cooperate 250g borax, 250g boric acid and 20g Sodium dodecylbenzene sulfonate and 5g sodium phosphite, being heated to preceding method becomes transparent liquid more than 80 ℃.Solubleness is 100%, drying machine is set in 120 ℃ again, dry 3 hours, makes moisture reach 5%.This material can be ground into fine powder below 200 orders with ball mill.The powder of the solubleness=500/250+250=100% of boronic acid compounds can easily create.

Embodiment 18

The solubleness that shows boronic acid compounds is the experimental result of 200% (200g/100cc water).

Mix 45g surfactant polyethylene maleate in 500g water, and stir, be heated to 85 ℃, add the 600g borax, the limit heating edge adds the 25g Sodium Fluoride again.Add 400g boric acid more therein, carry out high-speed stirring and mix.When reaching more than 80 ℃, become clear solution.Even do not add inorganic acids, still can become pH is 6.93, and proportion is 1.37 high concentration of boric acid compound solution (1000g/500g water), does not produce under 20 ℃ and separates out precipitation, keeps vitreous state.Yet after the static a few days, on container inner wall, produce cured body.On the other hand, in the clear solution of under above-mentioned 80 ℃, being dissolved into, limit high-speed stirring limit mixing 100g 15% (Si, BH ₃, K) MH type silanol salts solution.This solution is even prolonged preservation (30 days) is still clear solution.

Embodiment 19

In embodiment 18; with negatively charged ion series Sodium dodecylbenzene sulfonate (F-25), the sodium alkyl naphthalene sulfonate of tensio-active agent and representational sequestrant, NTA, xitix Na, tensio-active agent, also have stearyl-alkyl dimethyl ammonium chloride, neutral propylene glycol, the ethylene glycol of positively charged ion series to mix to use that also it doesn't matter.

Embodiment 20

In the NO-MO solution of 20% solids component boronic acid compounds, the tube interior (Japan dyeing Co., Ltd. system) that adds 1% carboxymethyl cellulose (CMC) (the first industrial pharmacy system) the roller coating machine of packing into, with 125g flaxen fiber (ト ス コ Co., Ltd. system) roll film, speed with per minute 10m is flooded, extract with cylinder, 120 ℃ dry down.

The test-results (test-results at engineering test center, Prefectura de Kanagawa) of fibre product combustion test method A-2 (Mei Keer combustion method) is:

Carbonization area 16cm ² Residual flame 0

Carbonization length 5.5cm residual grey 0

Be equivalent to non-fire material.To the paper wallpaper of Japan's system, also obtain residual flame, residual ash and be zero result.

Embodiment 21

According to embodiment 13, carry out following composite test (representing) with abbreviation.

Sodium Fluoride (NF), sodium phosphite (NP), S-WAT (NS), Sodium Nitrite (NO).

When regulation is used above-mentioned substance, the mineral acid of silane alkoxide (water-based is made the film mineral compound) is defined as:

Sodium Fluoride (MF), boric acid silanol (MH), sodium phosphite (MP), S-WAT (MS), Sodium Nitrite (MO) study solution of the present invention by the proportioning of embodiment 13.

Make up arbitrarily, NF-MF, NP-MP, NS-MS, NO-MO, NF-MH, NP-MH, NO-MP, NS-MH etc., but which kind of situation no matter become clear solution under 20 ℃, do not produce and do not separate out precipitation.These solution are coated on the sheet glass, and dry back is observed.Which kind of situation no matter, the crystallization completely dissolve of boronic acid compounds, and become flat board or be coated with membranaceous.

Embodiment 22

According to the conditions of mixture ratios of water 500cc, sodium polyacrylate 20g, borax 600g, Sodium Fluoride 5g, boric acid 400g, boric acid silanol (MH) 100cc, obtaining pH is 6.9, and proportion is 1.45, and boronic acid compounds solubleness is 200% solution.

This solution is remained on 80 ℃, flood ABS, polyester, PP, PE again, make its drying, adhere to the processing of about 40% solids component.

PP, PE are carried out difficulty combustion test (HB), and the difficult combustion tests in 2 minutes that non-relatively handled thing carries out are carried out difficult combustion test in 7 minutes to object being treated.

ABS, polyester, in difficulty combustion test, obtain the result of V-O.

Embodiment 23

Boronic acid compounds solubleness below be shown be 300 ℃ embodiment.

In 500cc water, add 30g sodium polyacrylate, 20g sodium phosphite, be heated to 90 ℃.The stirring of heating (keeping 90 ℃) limit is continued on the limit, slowly sneaks into the 1000g borax.Then, the phosphoric acid that adds 50g 89% again.It is carried out high-speed mixing, become approximate transparent state.Then add 500g boric acid, high-speed stirring again.When continuing heating (keeping 90 ℃), become transparent liquid.To wherein adding 100gMP (mineral acid being taken as the silane alkoxide (Si, P, Na) of phosphoric acid),, continue to stir and finished in 5 minutes again 90 ℃ of heating down.When the temperature of solution is reduced to moment of 20 ℃, observe this solution, be vitreous state.

Embodiment 24

Use sodium polyacrylate (the system PS521 of Kao Corp) with sequestrant function as tensio-active agent.The above-mentioned sodium polyacrylate of 5g (PS521) is joined in the 500cc water, and remix 230g borax and 140g boric acid add the 3g Sodium Fluoride again, are heated to 80 ℃, add silane alkoxide (MF) solution of 30g 7% subsequently.This liquid is applied on the sheet glass, observes, become level and smooth filming, do not find to have crystal habit.

With above-mentioned identical, use sodium polyacrylate (PS 521).5g polypropylene sodium is joined in the 500cc water, mix the 230g borax therein, then add 20g condensed phosphoric acid (85% reagent), after neutralizing, add the 3g Sodium Fluoride again, silane alkoxide (MF) solution of 140g boric acid, 30g 7% continues heating.Be heated to 90 ℃ of end.This solution is applied on the sheet glass, observes,, become smoothly and film, do not find to have crystal habit with above-mentioned identical.

Embodiment 25

Be used among the embodiment 13 NF-MF type goods solution of the present invention of explanation, in solubleness is 150% boronic acid compounds solution, add 15g carboxymethyl cellulose (CMC), mix, stir.The coating amount of the Japanese sheet glass system of dipping is 200g/m in this mixing solutions ²Glasscloth, be placed on again on the polyethylene film, make its partial desiccation.The polyethylene film that is covered was thereon again placed 7.Descended dry 30 minutes at 120 ℃ subsequently, make its drying, adhere to the 60g solids component this moment.

With most advanced and sophisticated flame be 1000 ℃ burner near this hardening thing, produce fusing, burn.

With the goods solution of the present invention of above-mentioned NF-MF type, in solubleness is 150% boronic acid compounds solution, mix 25% the plain resin of melamine urea by weight, obtain mixing solutions.Use this mixing solutions, glass web is handled equally, placed 7, subsequently, heated 10 minutes down, obtain the heat embrittlement body at 150 ℃.

With goods solution of the present invention, can make the solubleness of boronic acid compounds become 20%～150%, obtain the qualified non-fire material goods (JIS specification, heating 20 minutes, TD θ 0) of the soft or hard of all size.

Embodiment 26

Being used in NF-MF type goods solution of the present invention of explanation among the embodiment 13, is that 30% boronic acid compounds solution descended dry 6 hours at 150 ℃ with solubleness, and it is solidified, and is ground into the powder of 50 μ m.The plastic material of 200 parts heavy this powder and 100 parts of weights is mixed, obtain mixture.With the 100 parts heavy this mixture and the polyvinyl chloride (PVC) of 300 parts of weights, 6 parts heavy tin series stablizer, 200 parts of heavy glass powder (ガ ラ ス チ ヨ Star プ) mix, and make the thick SMC thin slice of 3mm with cylinder again.When this SMC thin slice is carried out UL difficulty combustion test, confirm that these goods have V-O level from extinguishing property.When carrying out combustion test, can confirm that smog and chlorine significantly reduce.

Under 180 ℃, above-mentioned SMC wafer processes can be become safety helmet.

Embodiment 27

Being used among the embodiment 13 NF-MF type goods solution of the present invention of explanation, is 100% boronic acid compounds solution with solubleness, 105 ℃ dry 3 hours down.Measure the dry product obtain like this, can confirm to contain 36% the solids component of having an appointment this moment.

With the above-mentioned dry product that contains 36% solids component, mix with equivalent weight and polycarbonate, and make its drying, obtain being attached with the resin of the present invention's product.Make ABS, saturated polyester, polystyrene and the above-mentioned dry product mixing that 36% solids component is arranged with equivalent weight equally, and make its drying, obtain adhering to the resin of the present invention's product respectively.

For 4 kinds of resins of such acquisition, carry out processing experiment with the test grinding machine (テ ス ト ラ ボ ミ Le) of the smart machine of Japan, all there is not unusual phenomenon this moment.

These 4 kinds of resins are made test film, carry out difficulty combustion test (UL-V), can be confirmed to be V-O level goods.And do not use nonflammable material in the past fully, only produce a small amount of decomposition gas and smog through heating.

Embodiment 28

The solution of the high concentration of boric acid compound various of the present invention of the explanation in the foregoing description is carried out drying, obtain containing solids component and be the goods more than 10%.When this goods and polyvinyl alcohol, latex mixing, produce gel.From this gel, squeeze out remainder water, can confirm that this residual product are the difficulty combustion goods that have from the performance of going out.

Moreover, when in the goods of above-mentioned this gelation, adding 1～10% zinc oxide, can produce caoutchouc elasticity.

Embodiment 29

Even below show also uncongealable in the winter time goods solution example of the present invention.

Use polypropylene glycol (PPG), polyethylene (PE) modulation goods solution of the present invention, even at 5 ℃, also can not freeze in the time of 0 ℃ this moment.

The modulation of goods solution of the present invention is undertaken by following 4 kinds of mixing ratios.Proportioning is g by weight, and each proportioning example carries out proportioning in proper order by proportioning shown in the left side entirely.

Proportioning order mixing ratio 1 mixing ratio 2 mixing ratios 3 mixing ratios 4

Water 500 500 500 500

EDTA 4 4

PEG20000 6 5

PPG1900 7 7

NF 10 10

NP 2 5

BN 230 230 230 230

P 20 20 20 20

BA 140 140 140 140

MF 30 30 30

MP 40

Each proportioning example all is defined in and carries out hydro-thermal reaction under 80 ℃.

After reaction finishes, in 5 ℃ refrigerator chamber, kept 10 hours, confirm not separate out, keep down still not producing in 5 hours at 5 ℃ again and separate out.

Can make under normal temperature (20 ℃) according to the present invention, not separate out and precipitate generation, solubleness is 100～300%, and stable high concentration solution in the time of can also being provided at drying, can carry out amorphous high concentration of boric acid compound of filming.Have, according to the present invention, the aqueous solution of high concentration of boric acid compound can be adjusted arbitrarily between pH4～pH8 again.

According to the present invention, use the fireproof material that contains the high concentration of boric acid compound, natural resource such as timber and natural fiber are utilized effectively, the fireproof material of having optimized global environment because of nuisanceless is provided.

Claims (11)

1. high concentration of boric acid compound, it is characterized in that: at the aqueous solution of the aqueous solution of metal ion end-capping reagent or moistening impregnability tensio-active agent in any, mix boronic acid compounds in the mode that solubleness at normal temperatures is equivalent to more than the 5g/100g water, this mixture is obtained carrying out hydro-thermal reaction more than 60 ℃.

2. high concentration of boric acid compound, it is characterized in that: at the aqueous solution of metal ion end-capping reagent or moistening impregnability water phase surfactant mixture in any, mix boronic acid compounds in the mode that solubleness at normal temperatures is equivalent to more than the 5g/100g water, this mixture is being carried out hydro-thermal reaction more than 60 ℃, adding phosphoric acid again or contain any in the silane alkoxide of siloxane backbone or two kinds and obtain.

3. high concentration of boric acid compound, it is characterized in that: at the aqueous solution of metal ion end-capping reagent or moistening impregnability water phase surfactant mixture in any, mix boronic acid compounds in the mode that solubleness at normal temperatures is equivalent to more than the 5g/100g water, add slightly acidic or weakly alkaline inorganic acid salt therein, this mixture is obtained carrying out hydro-thermal reaction more than 60 ℃.

4. high concentration of boric acid compound, it is characterized in that: at the aqueous solution of the aqueous solution of metal ion end-capping reagent or moistening impregnability tensio-active agent in any, mix boronic acid compounds in the mode that solubleness at normal temperatures is equivalent to more than the 5g/100g water, add slightly acidic or weakly alkaline inorganic acid salt therein, this mixture is being carried out hydro-thermal reaction more than 60 ℃, adding phosphoric acid again or contain any in the silane alkoxide of siloxane backbone or two kinds and obtain.

5. contain the composition that the fireproof of the high concentration of boric acid compound that claim 1 puts down in writing in each to the claim 4 is used.

6. fire-resistant fire-retardant material, it is characterized in that: the fireproof composition that will contain the high concentration of boric acid compound of each record in the claim 1 to 4, normal pressure is injected in employing, and combined the soaking of method that pressurization is injected or decompression is injected is contained in timber, this drying of wood obtained again.7. fireproof material, it is characterized in that, any with synthetic resins or latex, with any of isocyanate group or zinc oxide or contain isocyanate group or the composition of zinc oxide carries out compound, again with contain claim 1 to 4 in the fireproof of high concentration of boric acid compound of each record mix mutually with composition, with its coating or soak to contain and be coated on fibre product, wood chip, woodwork, paper product or inorganic plate-shaped products any, under normal temperature or heating, carry out drying and obtain.

8. matrix material is characterized in that: the fireproof of the high concentration of boric acid compound of each record in containing claim 1 to 4 is with in the composition, adds thermosetting resin and obtains.

9. fireproof material, it is characterized in that: the fireproof of high concentration of boric acid compound that will contain each record in the claim 1 to 4 is with after composition, coating, flooding or be infused on fibre product, paper product or the woodwork, carries out drying and obtains.

10. fireproof material, it is characterized in that: the fireproof composition that will contain the high concentration of boric acid compound of each record in the claim 1 to 4 is coated on the surface of synthetic resin solid thing, silicone resin or fluoro-resin or sneaks into wherein, carry out drying, make its Nai Gaore.

11. fireproof material, it is characterized in that: the fireproof composition that will contain the high concentration of boric acid compound of each record in the claim 1 to 4, soak and be contained on inorganic or organic textiles or the non-textile, be made into semiarid preformed flitch or exsiccant laminated die plastic compound.

12. fireproof material, it is characterized in that: will contain the fireproof composition of high concentration of boric acid compound of each record in the claim 1 to 4 and any mixing in carboxymethyl cellulose or the carboxymethyl hydroxyethyl cellulose, it is soaked be contained on inorganic or organic textiles or the non-textile, be made into semiarid preliminary shaping flitch or exsiccant laminated die plastic compound.

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