JP2012081603A - Flame retardant wood, quasi-noncombustible wood, and noncombustible wood - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a noncombustible wood that is sufficiently able to pass heat generation tests in conformity with the revised Building Standards Act, regarding wood flame retardation/noncombustiblization agent using boric acid.SOLUTION: A cut end of a wood is washed by using high-speed cleaning water, and this wood is immersed in a pool stored with hot water of about 50 to 60°C for about 60 hours. Meanwhile, an agent is obtained by: (a) throwing polyphosphoric acid [HPO] into hot water of 50°C or higher; (b) throwing next diammonium phosphate into it after the polyphosphoric acid is completely dissolved and stir-dissolving the diammonium phosphate, while keeping this temperature; (c) throwing boric acid into it after the diammonium phosphate is dissolved and stir-dissolving the boric acid, while keeping the temperature; and (d) throwing next phosphoric acid into it and dissolving the phosphoric acid. This agent is injected into the wood from which the impregnated hot water has been extraction-removed. This immersion injection is continued for 60 to 120 hours while keeping the temperature at 50 to 60°C. Then, after washing it by using high-speed washing water, it is cured in the sun for 10 to 20 days. Then, it is subjected to a forced drying processing for 7 to 20 days in a drying machine at 30 to 40°C. Consequently, the noncombustible wood is obtained.

Description

  The present invention relates to a construction wood, a flame retardant / quasi-flame retardant / flame retardant chemical agent used for making it non-flammable / quasi-flame retardant / flame retardant, and flame retardant / quasi-flame retardant / flame retardant by this chemical. Regarding wood.

According to the Building Standards Law revised in 1998, the calorific value when a substance burns is measured using a cone calorimeter that is based on the weight consumption of oxygen based on the requirement that 13.1 MJ per kg of oxygen. If the heat generation satisfies the following conditions, even wood can be used as various flame retardant materials, quasi-incombustible materials, and incombustible materials as various building materials. That is, even when the heating part for burning the test body of the corn calorimeter is heated for 20 minutes,
(1) The total calorific value is 8 MJ / m ² or less.
(2) There should be no cracks or holes penetrating to the reverse side, which is harmful to fire prevention.
(3) The maximum heat generation rate should not exceed 200 kW / m ² for 10 seconds or more.
And if the above phenomenon does not appear even after 5 minutes, as "flame retardant material", if the above does not appear even after 10 minutes, as "quasi-incombustible material", and further after 20 minutes, If the phenomenon does not appear, it can be used as an “incombustible material”.
Among these, for example, a technique disclosed in Japanese Patent Application Publication No. 2001-527093 is known as a flame retardant / quasi-incombustible / incombustible technology for wood mainly using boric acid. The technology disclosed in Japanese Translation of PCT International Publication No. 2001-527093 relates to the invention title “Flame-retardant biocidal composition and method for producing the same”, “Providing a flame-retardant and biocidal composition that is easy to produce and use, and a method for producing the same” For that purpose (see the summary column of the publication), “The composition is boric acid (H ₃ BO ₃ ), borax (Na ₂ B ₄ O ₇ · 10H ₂ O or Na ₂ B ₄ O ₇ · 5H _{2 O),} a binder, and "(see the publication specification claim 1 by including water), it is to achieve cents above object.

JP-T-2001-527093

However, the wood incombustibility technique disclosed in JP-T-2001-527093 is based on boric acid (H ₃ BO ₃ ), borax (Na ₂ B ₄ O ₇ · 10H ₂ O, or Na ₂ B ₄ O ₇ · 5H _2. O) is used, but as pointed out in paragraph number 0002 of the above publication, there is a problem that “the manufacture and use of these compositions are usually troublesome” (same as above). Publication specification paragraph number 0002).
The inventor of the present application intensively studied flame retardant / quasi-incombustible / non-flammable technology mainly using boric acid, making the wood using boric acid, which is considered difficult in the past, flame retardant / quasi-incombustible / Incombustibility, quasi-incombustibility, and incombustibility that can withstand the revised Building Standard Act in the exothermic test of corn calorimeters by completing incombustible chemicals and treating wood with incombustibles The purpose is to provide wood.

In order to achieve the above-mentioned object, the invention according to claim 1 of the present application is a non-combustible wood, wherein the lumber lumber is washed with high-speed washing water, and then immersed in a hot water pool of about 50 to 60 ° C. for 60 hours inside and outside. Then, after draining the hot water, (a) pouring polyphosphoric acid (H _{(n + 2)} P _n O _{(3n + 1)} ) into hot water of 50 ° C. or higher, and (b) the polyphosphoric acid ( When H _{(n + 2)} P _n O _{(3n + 1)} ) is completely dissolved, the temperature is maintained, diammonium phosphate ((NH ₄ ) ₃ HPO ₄ ) is added, and stirred to dissolve (c ) Once this is dissolved, while maintaining the temperature, add boric acid (boric acid: H ₃ BO ₃ ), stir to dissolve, (d) then add phosphoric acid (H ₃ PO ₄ ) to the dissolved water Then, the dissolved drug is injected and kept at a temperature of 50 to 60 ° C. for 60 to 120 hours. , After immersion in the chemical, after washing with high-speed washing water, curing for 10 to 20 days in the sun, and then forcibly drying for 7 to 20 days in a dryer at 30 to 40 ° C When a non-combustible treated wood specimen is heated for 20 minutes with a 25 mm gap between the surface of the specimen and a cone heater that enables a heat radiation amount of 50.0 KW / m ² , (1) 8MJ / m ² or less, (2) No cracks or holes penetrating to the back side, which is harmful to fire prevention, and (3) The maximum heat generation rate does not exceed 200kw / m ² for 10 seconds or more. It is characterized by.
The invention according to claim 2 of the present application. In the non-combustible wood according to claim 1, the chemical injection is purified by the order and method according to claim 1 when the chemical concentration becomes 1.3 or less based on a specific gravity of about 1.3. Injecting the drug that has been carried out, injecting water when it becomes 1.3 or more, and continuing the immersion for 60 hours to 120 hours at a temperature of 50 to 60 ° C. while maintaining the specific gravity 1.3, It is a non-combustible treated wood that has been washed with high-speed washing water, cured for 10 to 20 days in the sun, and then subjected to forced drying treatment for 7 to 20 days in a dryer at 30 to 40 ° C. It is characterized by that.

  A flame retardant / incombustible chemical for wood that mainly uses boric acid can be completed, and the corn calorimeter exothermic test has been revised by using this chemical to make the wood flame retardant / incombustible. We were able to make it a flame retardant, quasi-incombustible, and non-flammable wood that complies with the flame retardant, quasi-incombustible and non-flammable certifications stipulated in the Building Standards Act.

FIG. 1 is a diagram showing a schematic configuration of a corn calorimeter Corn calorimeter test result graph Corn calorimeter test result graph

As described above, it has been difficult to produce a chemical (composition) that achieves flame retardant / incombustibility of wood mainly composed of boric acid. However, by purifying the wood flame-retardant / flame-retardant agent according to the following procedure, the wood flame-retardant / flame-retardant agent using boric acid was completed, and the wood was also made non-flammable. By performing the treatment, incombustible wood that can sufficiently withstand the revised Building Standard Law in the exothermic test of the corn calorimeter can be obtained.
Hereinafter, an example of the purification of the wood incombustible chemical according to the present invention will be described.

[Purification of incombustible chemicals for wood]
In order to make a drug mainly composed of high-concentration boric acid, it is necessary to strictly select the temperature control and the order in which the drugs are dissolved.
(1) First, polyphosphoric acid (H _{(n + 2)} P _n O _{(3n + 1)} ) is put into warm water of 50 ° C. or higher.
(2) Next, when the polyphosphoric acid (H _{(n + 2)} P _n O _{(3n + 1)} ) is completely dissolved, the temperature is maintained and diammonium phosphate ((NH ₄ ) ₃ HPO ₄ ) is added. Add and stir to dissolve.
(3) When this is dissolved, while keeping the temperature, boric acid (boric acid: H ₃ BO ₃ ) is added and dissolved by stirring.
(4) Next, phosphoric acid (H ₃ PO ₄ ) is added to the dissolved water and dissolved.
In this way, “refining non-combustible chemicals for wood. In order to achieve high-concentration phosphate dissolution, temperature control and the order of the above-mentioned chemicals are essential. High concentration of dissolved water cannot be obtained.

[Immersion of wood in incombustible chemicals]
(1) A timber obtained by sawing a raw wood into a predetermined size (for example, 15 mm × 105 mm × 2000 mm), for example, cedar and firewood is used as the timber.
The lumber to be lumbered is also called a domestically produced green material, and usually a natural drying material of one year is used. The wood that had been forced to dry had poor results.
(2) First, the lumber lumber lumber is washed with high-speed washing water. This is to efficiently absorb the drug from the end of the mouth.
(3) Next, a predetermined amount of wood (usually: 2m ³ = about 640 pieces) is immersed in a hot water pool at about 50 to 60 ° C. for 60 hours. This is to remove the wood from the wood.
(4) Once hot water is extracted from the pool, the above-mentioned drug is injected into the pool, and maintained at a temperature of 50 to 60 ° C. for 60 to 120 hours (normally 3 days (73 hours) in a normal state). Continue soaking while measuring the concentration of the sample with a densitometer. Concentration is measured with a hydrometer. When it becomes thinner with a specific gravity of about 1.3 as a reference, the medicine is injected, and when it is thick, water is injected to continue the immersion. In this case, a slightly lower concentration is sufficient in the summer when the room temperature is high, but in winter when the room temperature is low, the wood "non-combustible material" that can withstand the revised Building Standards Act in the exothermic test of the corn calorimeter Can not.
(5) When the above chemical immersion is completed, after washing with high-speed washing water as described above, curing is carried out for 10 to 20 days in the sun.
(6) Then, after completion of curing, forced drying treatment is performed for 7 to 20 days in a dryer at 30 to 40 ° C.
(7) After forced drying, pack as a product and prepare for shipment.

[Cone calorimeter exothermic test]
(Exothermic test 1)
The cone calorimeter has the following general structure. That is, the cone calorimeter includes a heating unit that heats the specimen, an exhaust part that repairs the combustion gas generated from the specimen, and a measurement unit that measures the oxygen gas concentration, temperature, and flow rate in the exhaust. FIG. 1 is a diagram showing a schematic configuration of a cone calorimeter. As described above, the cone calorimeter is mainly composed of a heating part (A), an exhaust part (B), and a measurement part (C). Body, 2 is a sample holder, 3 is a cone heater, 4 is a load cell, 5 is an exhaust hood, 6 is an exhaust blower, 7 is an orifice flow meter, and 8 is a laser smoke concentration meter. , 9 is a gas sampling device, and 10 is a gas analyzer.
The test body 1 is made of non-combustible cedar wood having a thickness of about 12 mm and a heating surface cut out to about 0.01 m ² .

  The sample holder 2 is a holder for placing a test body (sample) 1 within 100 × 100 × 50 mm, and the cone heater 3 is a conical heater capable of setting a radiation amount of 0 to 100 Kw. Further, the load cell (load meter) 4 for measuring the weight change of the test body 1 can measure a maximum of about 1 kg of sample using a 5 kg load cell. Further, the exhaust hood 5 should be called a smoke collection hood, and can collect all the smoke emitted from the test body 1.

The exhaust blower 6 includes a blower motor that makes the exhaust flow rate constant, and can adapt the flow rate to 0.024 m ² / sec at room temperature. The orifice flowmeter 7 is an orifice having a diameter D0 [m] and a circular hole cross-sectional area A0 [m ² ] in the center in a straight pipe having a pipe inner diameter D1 [m] and a channel cross-sectional area A1 [m ² ]. The plate has a structure in which the fluid flowing in the pipe passes through this circular hole, and as a result, the cross-sectional area of the flow path is reduced, the flow velocity is increased, and the static pressure on the downstream side is reduced.
Since the static pressure drop is substantially proportional to the flow rate, the flow rate of the fluid flowing in the pipe can be determined by measuring the pressure difference (differential pressure) before and after the orifice plate.

  The laser smoke densitometer 8 can measure the smoke concentration using 1.0 mWHe-Ne laser light. Further, the gas sampling device 9 is a device for sampling the surrounding gas, and the sampled gas is converted into oxygen consumption (oxygen reduction amount) when the specimen 1 is burned by the gas analyzer 10. ).

  Using the corn calorimeter having such a basic configuration, the wood subjected to the above-mentioned chemical immersion, washing, sun drying and forced drying was tested. That is, as the corn calorimeter, a corn calorimeter 3 (model C3) manufactured by Toyo Seiki Seisakusho Co., Ltd. was used, and the treated specimen 1 having the following predetermined dimensions was placed on the sample holder 2, A cone calorimeter test was performed by heating the specimen 1 with the cone heater 3.

  However, since the cone calorimeter requires strict measurement of oxygen consumption, the surrounding oxygen concentration before and after the measurement must be accurately measured. For this reason, first, in order to measure with a cone calorimeter, calibration at the start of measurement is essential. As described above, the corn calorimeter heats the specimen and precisely measures the amount of oxygen consumed there. Therefore, the effects of oxygen concentration, temperature, and humidity in the corn calorimeter are greatly reflected. Therefore, at least the oxygen concentration, temperature, and humidity must be measured in advance as the cone calibration element.

  Table 1 shows the results of a corn calorimeter test of incombustible cedar wood carried out on February 3, 2010.

(Test conditions)
The test conditions are as follows. First, this test is a test of whether or not it corresponds to the “non-combustible” certification test stipulated in the Building Standards Act described above. As the test body 1, the “non-combustible cedar” treated in Example 1 has a surface area of 0.010000 m. ^2. A test body 1 having a thickness of 12.00 mm and a mass of 90.00 g was prepared, and a holder cover (not shown) was placed on the sample holder having a mass of 475.94 g. The distance between the surface of the body 1 and the heater 3 was set 25 mm apart. Note that the holder cover (not shown) is for heating only the surface of the test body 1, and the sample holder mass includes the cover mass.

Then, the cone heater 3 is energized, the temperature of the heater 3 that secures a heat radiation amount of 50.0 kW / m ² , 639.05 ° C. is measured, and the exhaust flow rate during the test is 0 0.024 m ³ / sec (exhaust temperature: 6.7 ° C., exhaust pressure: 124.946 Pa).
The room temperature at this time was 20 ° C., humidity 50%, and atmospheric pressure 1013 hPa. In this state, heating was performed for 1200 seconds (20.0 minutes), and the sampling interval was measured every 2 seconds.

(Conversion parameter)
In addition, in order to know the initial oxygen state described above, the calibration must be performed and conversion based on the calibration factor must be performed. Thus, the inherent conversion factor of this corn calorimeter is 13.100 MJ / Kg, the initial oxygen state (O ₂ base ain), the carbon monoxide state (CO baseline) and the carbon dioxide state (CO ₂ Baseline) was measured as 20.9494%, -0.00304%, and 0.0749%, respectively, and based on this, the calibration factor of 0.04542212 was obtained.

(Test results)
As a result, the following test results were obtained for this specimen 1.
(1) Total calorific value (THR): 2.80 MJ / m ²
(2) Maximum heat generation rate (HRR): 6.06 KW / m ² (at 858.10 seconds)
(3) Average heating rate (HRR): 2.33 KW / m ²
(4) Average heat generation rate T60: 2.19 KW / m ²
(5) Average heat generation rate T180: 1.43 kW / m ²
(6) Average heat generation rate T300: 1.20 KW / m ²
(7) Final sample mass: 39.17 g
(8) Sample mass reduction: 50.83 g
In this test, the test body 1 was not ignited, and therefore the flame was not extinguished.
Also,
(9) Neither cracks nor through-holes reaching the back surface of the test body 1 occurred.
further,
(10) 200K excess duration: 0.0 sec
(11) Total time exceeding 200K: 0.0 sec
As a result, in this study,
(A) Average combustion effective heating value (HOC): 0.55 MJ / Kg
(B) Average mass reduction rate (MLR): 4.150 g / s · m ²
(C) Average CO yield: 0.01612 kg / kg
(D) Average CO ₂ yield: kg / kg
Got.

When this test result is displayed as a graph for each heating time, it is as shown in FIG.
In FIG. 2, the alternate long and short dash line indicates the heat generation rate (KW / m ² ), the dotted line indicates the mass (g), the broken line indicates the oxygen (O ₂ ) displacement (%), and the solid line indicates the total calorific value (MJ / m ² ). (× 10) is shown, and the horizontal axis indicates the heating time (min).

(Exothermic test 2)

  Table 2 shows the corn calorimeter test result of the incombustible cedar test body 1 which was implemented on August 20, 2010.

(Test conditions)
As described above, the test condition is a test of the “non-combustible cedar” test body as to whether it corresponds to the “non-combustible” certification test stipulated in the Building Standard Law.
Similarly, as the test body 1, the test body 1 having a surface area of 0.010000 m ² , a thickness of 15.00 mm, and a mass of 105.00 g was prepared from the “non-combustible cedar” treated in Example 1, and the mass of 2.64 g was measured. The sample holder was placed on the sample holder without attaching a holder cover (not shown), and the distance between the surface of the specimen 1 and the heater 3 was set 25 mm apart. Note that measuring without a holder cover results in a slight decrease in test data, but even without a holder cover, data that meets the certification standards can be obtained as will be described later. Therefore, it is possible to measure without the holder cover, and this exothermic test 2 is measured without attaching the holder cover.

Then, the cone heater 3 is energized, and in this test 2, the temperature of the heater 3 that secures a heat radiation amount of 50.0 KW / m 2 is measured, and the exhaust flow rate during the test is measured. Was 0.024 m ³ / sec (exhaust temperature: 29.8 ° C., exhaust pressure: 111.178 Pa).
The room temperature at this time was 20 ° C., humidity 50%, and atmospheric pressure 1013 hPa. In this state, heating was performed for 1200 seconds (20.0 minutes), and the sampling interval was measured every 2 seconds.

(Conversion parameter)
As described above, the inherent conversion factor of this corn calorimeter is 13.100 MJ / Kg, and the initial oxygen state (O ₂ base Ain) is 20.9494%. Based on this, the calibration factor is 0.04645239 was determined. The carbon monoxide state, (CO baseline), and carbon dioxide state (CO ₂ baseline) were not measured because combustion ignition did not occur in the previous tests.

(Test results)
As a result, the following test results were obtained for this specimen 1.
(1) Total calorific value (THR): 7.57 MJ / m ²
(2) Maximum heat generation rate (HRR): 11.10 KW / m ² (at 1140.10 seconds)
(3) Average heating rate (HRR): 6.38 KW / m ²
(4) Average heat generation rate T60: 0.25 KW / m ²
(5) Average heat generation rate T180: 0.46 KW / m ²
(6) Average heat generation rate T300: 1.24 KW / m ²
(7) Final sample mass: 53.44 g
(8) Sample mass reduction: 51.56 g
In this test, the test body 1 did not ignite and therefore did not extinguish.
Also,
(9) Neither cracks nor through-holes reaching the back surface of the test body 1 occurred.
further,
(10) 200K excess duration: 0.0 sec
(11) Total time exceeding 200K: 0.0 sec
As a result, in this study,
(A) Average combustion effective heating value (HOC): 1.47 MJ / Kg
(B) Average mass reduction rate (MLR): 4.623 g / s · m ²
Got.

In the cone calorimeter used, ignition combustion does not occur at the above-mentioned amount of radiant heat, so the carbon monoxide state, (CO base line), and carbon dioxide state (CO ₂ base line) are not measured. Neither “(C) average CO yield” nor “(D) average CO ₂ yield” is measured.

When this test result is displayed as a graph for each heating time, it is as shown in FIG.
In FIG. 3, as in FIG. 2, the alternate long and short dash line indicates the heat generation rate (KW / m ² ), the dotted line indicates the mass (g), the wavy line indicates the oxygen (O ₂ ) displacement (%), and the solid line indicates the total calorific value ( MJ / m ² ) (× 10), and the horizontal axis represents the heating time (min).

As is clear from the corn calorimeter test results shown in FIG. 2 and the corn calorimeter test results shown in FIG. 3, the total calorific value (indicated by the solid line) is 2.80 MJ / m ² , 7.57 MJ / m ² , and does not exceed 8.0 MJ / m ² , and “(9) Neither cracks nor through-holes reaching the back surface of the test body 1 occurs” and “(10) Since both “200K excess duration” and “(11) 200K excess total time” are both zero, therefore, the test piece 1 is the following building even when heated for 20 minutes in a cone calorimeter It is clear that the non-combustibility standards stipulated in the Standard Law are fully met.

(1) The total calorific value is 8 MJ / m ² or less.
(2) There should be no cracks or holes penetrating to the reverse side, which is harmful to fire prevention.
(3) The maximum heat generation rate should not exceed 200 kW / m ² for 10 seconds or more.

  INDUSTRIAL APPLICABILITY The present invention can be used for flame retardant, semi-incombustible, and non-combustible wood that conform to the Building Standard Law.

DESCRIPTION OF SYMBOLS 1 Test body 2 Sample holder 3 Cone heater 4 Load cell 5 Exhaust hood 6 Exhaust blower 7 Orifice flow meter 8 Laser smoke concentration meter 9 Gas sampling device 10 Gas analyzer

Claims (2)

The lumber timber mouthpiece is washed with high-speed washing water, then immersed in a hot water pool at about 50 to 60 ° C. for 60 hours, and then the hot water is drained, and then (a) polyphosphoric acid in hot water at 50 ° C. or higher. (H _{(n + 2)} P _n O _{(3n + 1)} ), (b) Then, when the polyphosphoric acid (H _{(n + 2)} P _n O _{(3n + 1)} ) is completely dissolved, While maintaining the temperature, diammonium phosphate ((NH ₄ ) ₃ HPO ₄ ) was added and dissolved by stirring. (C) Once dissolved, boric acid (boric acid: H ₃ BO ₃ ) was maintained while maintaining the temperature. (D) Next, a drug dissolved by adding phosphoric acid (H ₃ PO ₄ ) into the dissolved water is injected, and a temperature of 50 to 60 ° C. is maintained. Continue soaking for 120 to 120 hours, soak in chemicals, wash with high-speed washing water, and then cultivate in the sun for 10 to 20 days And, further, thereafter, the test of 30 ° C. to 40 ° C. in the dryer at 7 days and 20 days forced drying process the incombustible treated wood Been of the heat radiation amount of the specimen surface and 50.0KW / ^{m 2} When heated for 20 minutes with a 25 mm gap between the cone heaters that can be used, (1) the total calorific value is 8 MJ / m ² or less, and (2) cracks and holes that penetrate to the rear side that are harmful to fire prevention. (3) Non-combustible wood characterized in that the maximum heat generation rate does not exceed 200 kw / m ² continuously for 10 seconds or more. The drug injection is performed by injecting a drug purified by the sequence / method according to claim 1 when the drug concentration becomes 1.3 or less based on a specific gravity of about 1.3. In the case of 3 or more, water is injected, and the immersion is continued for 60 hours to 120 hours at a temperature of 50 to 60 ° C. while maintaining a specific gravity of 1.3. It is a non-combustible treated wood which has been cured for 10 to 20 days in a day, and further subjected to forced drying treatment for 7 to 20 days in a dryer at 30 to 40 ° C. Incombustible wood.

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